THE PREPARATION ANDSTRUCTURAL? .

CHARACTERIZATION or momUM __i _j .~T ~. 5 5
AND IANTALUMCOMPLEXES '1. .5,
WITH DIPIVALOYtMIET-HAME ‘  

Thesis for the Degree of Ph. D,
MICHIGAN STATE UNIVERSITY
GEORGE PODOLSKY
1972

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thesis entitled

THE PREPARATION AND STRUCTURAL CHARACTERIZATION
OF NIOBIUM AND TANTALUM COMPLEXES WITH DIPIVALOYLMETHANE

presented by

George Podolsky

has been accepted towards fulfillment
of the requirements for

Ph .D . degree in 121191111311!-

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ABSTRACT
THE PREPARATION AND STRUCTURAL CHARACTERIZATION

OF NIOBIUM AND TANTALUM COMPLEXES WITH DIPIVALOYLMETHANE

By

George Podolsky

A new series of Nb(V) and Ta(V) dipivaloylmethanate (DPM) complexes
have been prepared and characterized. Complexes of the type M(DPM)C14 and
M(DPM)éC13 were obtained by allowing the metal pentahalide to react with
neat H(DPM) (M 3 Ta) and with H(DPM) in the presence of dichloromethane as
a solvent (M - Nb). The complexes of the M(DP'M)C14 series exhibit
similar infrared and nmr spectra, but the Nb derivative appears to be
much less stable in solution in the absence of free ligand. The spectral
similarities and differences in stability for the Nb and Ta derivatives
also hold true for the M(DPM)2013 complexes. Conductivity data indicate
that Ta(DPM)2C13 is highly dissociated in nitrobenzene and in nitro-
methane solution; a dissociation equilibrium involving Ta(DPM)4+ and

TaCl6- is suggested. The constitution of the M(DPM)ZC complexes in

13
the solid state may correspond to an eight-coordinate cationic salt,
[M(DPM)4][MC16]. Evidence to support this formulation is based
primarily on the presence of a band in the ir spectrum near that
expected for TaCl6-. The inability to obtain a higher substitution
product in the presence of a large excess of ligand or in the presence
of a base also suggests the ionic constitution of the complex. An
attempt to prepare the Nb(DPM)4+ cation by reaction of Nb(DPM)4 and

anhydrous, oxygen~free Cl in CC14 led to abstraction of ligand

2

oxygen by the metal and the formation of a polymeric oxo-complex,
[NbOClz(DPM)]x.

A new, stable Nb(IV) complex Nb(DPM)4 was also discovered. This
unusual eight-coordinate (11 metal ion complex was amenable to characteri-
zation by various forms of spectroscopy, both in the solid state and in
solution. An X—ray structure determination of the complex showed that
the coordination polyhedron of the molecule is best described by the D4
square antiprism, a previously unreported stereoisomer for eight-
coordination chemistry. Further studies including electronic absorption
and esr SpectroscOpy indicate that the Nb(DPM)4 molecule retains its

square antiprismatic stereochemistry in solution.

THE PREPARATION AND STRUCTURAL CHARACTERIZATION

OF NIOBIUM AND TANTALUM COMPLEXES WITH DIPIVALOYLMETHANE

By

George Podolsky

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements

for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1972

To Rita

ii

ACKNOWLEDGEMENTS

The author wishes to thank Professor Thomas J. Pinnavaia for his
motivation and assistance during this study.

Gratitude is also due to Professor Alexander Tulinsky and his
group, especially Dr. Pene10pe W. Codding and Mr. Richard L. Vandlen
for their aid in the crystal structure determination.

The author is also deeply grateful to his wife, Rita, for her
patience and unrelenting encouragement and to his parents and his

wife's parents for their aid.

iii

II.

III.

IV.

VI.

TABLE OF CONTENTS

Statement of Purpose . . . . . . . . . . . . . . .

Survey of Niobium and Tantalum Beta-Diketonate
Chanistry O I O O O O O O O O O O O O O O O O O O 0

Experimental Section . . . . . . . . . . . . . . .

A. Reagents . . . . . . . . . . . . . . . . . . .
B. General Techniques Used in the Reactions of
Metal Halides. . . . . . . . . . . . . . . . .
C. Purification of Niobium Pentachloride. . . . .
D. Syntheses. . . . . . . . . . . . . . . . . . .
E. Physical Methods of Characterization . . . . .

Results and Discussion . . . . . . . . . . . . . .

A. Tantalum(V) and Niobium(V) Derivatives of
Dipivaloylmethane. . . . . . . . . . . . . . .
B. Preparation and Characterization of
Tetrakis(dipivaloylmethanato)niobium(IV) . . .
C. The X-Ray Structure Determination of Nb(DPM)4.
D. The Stereochemistry of Nb(DPM)4 in Solution. .

Bibliography 0 O O O O O O O O O O O O O O O O O O
Appendices . . . . . . . . . . . . . . . . . . . .

A. Diketonate Ligand Abbreviations . . . . . . . .
B. The Observed and Calculated Structure Factors
(Multiplied by 10 and Using a Scale Factor
of 0.9453). . . . . . . . . . . . . . . . . . .
C. Interior Angles of the Planes Comprising th D
Square Antiprismatic Polyhedron of Nb(DPM)4 . .

iv

Page

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. A
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. ll
. 12
. 16
. l6
. 24
. 32
, 32
, 68
, 72
, 119
. 146
i

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. ii
.xxvii

Table

IIA.

IIB.

III.

IV.

VI.

VII.

VIII.

IX.

XI.

XII.

XIII.

XIV.

LIST OF TABLES

Chemical Analyses for Products Obtained From the
Reactions of TaClS and NbC15 With Dipivaloylmethane

Final Atomic Coordinates and Thermal Parameters
for Nb(DPM)4o o o o o o o o o o o o o o o o o o o 0

Electron Densities (p) for Atoms Comprising the
Chelate Rings in Nb(DPM)4 . . . . . . . . . . . . .

Nb—O and 0-0 Distances (A) in Nb(DPM)4. . . . . . .
DPM Ligand Bond Distances (A) in Nb(DPM)4 . . . . .
O-Nb-O Angles in Nb(DPM)4 . . . . . . . . . . . . .
Chelate Ring Interior Angles in Nb(DPM)4. . . . . .

Average Bond Distances and Angles in the Nb-DPM
Chelate Ring 0 O I O I O O O I O O O O O O 0 O I O O

Polyhedral Edge Lengths (A) When Nb(DPM)4 is Viewed
as a D2(aabb) Dodecahedron. . . . . . . . . . . . .

Polyhedral Edge Lengths (3) When Nb(DPM)4 is Viewed
a D2(gggg) Dodecahedron . . . . . . . . . . . . . .

Polyhedral Edge Lengths (A) When Nb(DPM)4 is Viewed
3 D4(£222) Square Antiprism . . . . . . . . . . . .

Deviations (A) of Oxygen Atoms from Best Trapezoidal
Planes and Angles of Intersection (oT) of the Planes
When Nb(DPM)4 is Viewed as a D2(aabb) Dodecahedron.

Deviations (A) of Oxygen Atoms from Best Trapezoidal
Planes and Angles of Intersection (oT) of the Planes

When Nb(DPM)4 is Viewed as a D2(gggg) Dodecahedron.

88

88

0
Deviations (A) of Oxygen Atoms from Best Square Planes,

Angles of Intersection (as) of the Planes, and the

Shape Parameter Angles (6) When Nb(DPM)4 is Viewed as

8 D4(£2’2£) square Antiprism o o o o o o o o o o o 0

Experimental and Most Favorable Polyhedron Shape
Parameters When Nb(DPM)4 is Viewed as a D2(aabb)

and D2(gggg) Dodecahedron and a D4(££££) Square Antiprism

V

Page

34

74

79
80
82
83

84

85

103

104

105

106

107

108

109

Table

XVII.

XVIII.

XIX.

LIST OF TABLES (cont'd)

Experimental and Idealized Plane Deviations (A)

and Angles of Intersection for Nb(DPM)4 Viewed as

a D4 Square Antiprism and a D2(aabb) and D2(gggg)
Dodecahedron . . . . . . . . . . . . . . . . . . . .

UV-Visible Bands of Nb(DPM)4 In Dichloromethane
(2.83 x 1.0-4 H) O O I O C C C C O O O O O I C O O 0

Second Order Correction Equations for Calculation of
g values 0 O C I O O O O O O O O O O O O O O O O O

ESR Parameters for Nb(DPM)4. . . . . . . . . . . . .

X-Ray Powder Patterns for Nb(DPM)4 and Zr(DPM)4. .

vi

Page

. 110

. 122

LIST OF FIGURES

Figure
1. The 9 possible stereoisomers for an eight-coordinate
tetrakis chelate . . . . . . . . . . . . . . . . . .
2. Apparatus assembly for handling anhydrous solutions
during syntheses . . . . . . . . . . . . . . . . . .
3. NMR tube assembly for Evans magnetic susceptibility
measurment O O O O O O O O O O O O O O O O O O O O 0
4. Infrared spectrum of Ta(DPM)C14 in a Nujol mull.
5. Room temperature nmr spectra of Ta(DPM)C14 in
diChlorome thane O O O O O O O O O O O I I O I O O O O
6. Room temperature nmr spectra of a dichloromethane
solution of the product isolated from the mother
liquor of the Ta(DPM)Cla synthesis . . . . . . . . .
7. Infrared spectrum of Ta(DPM)2C13 in a Nujol mull . .
8. Room temperature nmr spectra of Ta(DPM)2C13 in
dichloromethane. . . . . . . . . . . . . . . . . .
9. Infrared spectrum of Nb(DPM)Cl4 in a Nujol mull. . .
10. Room temperature nmr spectra of Nb(DPM)C14 in
diChloromethane O O O O O I O O O I O O O O O O O O O
11. Room temperature nmr spectra of Nb(DPM)C1 in
dichloromethane after the compound has been allowed
to hydrolyze in the solid state. . . . . . . . . . .
12. Infrared spectrum of Nb(DPM)2C13 in a Nujol mull
13. Room temperature nmr spectra of Nb(DPM)2Cl3 in
dichloromethane. . . . . . . . . . . . . . . . . .
14. Infrared spectrum of [NbOC12(DPM)]x in a Nujol mull.
15. Infrared spectrum of Nb(DPM)4 in a Nujol mull. . .
16a. The composite electron density along the b axis for
Nb(DPM)4, Mblecule A, showing the half of the
molecule containing ligands L1 and L2 . . . . . . .
16b. The composite electron density along the b axis

showing the half of Molecule A containing ligands
L3 and L4 0 O O I O O O O O O O O O O O O O O O O O 0

vii

Page

14

27

36

39

41

46

48

52

54

57

60

62

66

71

87

89

LIST OF FIGURES (cont'd)

Figure

17a.

17b.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.
28a.
28b.

29.

The composite electron density along the b axis for
Nb(DPM)4, Molecule B, showing the half of the
molecule containing ligands L1 and L2 . . . . . . . . .

The composite electron density along the b axis showing
the half of Molecule B containing ligands L3
and L4 0 O I O O O O O C O O O O I I I I O O O O O O O O

The motions associated with the transformation of a
cube to a D2d dodecahedron and D4d square antiprism. . .

A view of the "idealized" D4 square antiprismatic
coordination polyhedron down the "pseudo" C4 axis
including the numbering scheme for the ligands,

oxygen atoms and carbon atoms for Nb(DPM)4 . . . . . . .
The Board and Silverton polyhedral shape parameter
notation for the DZd dodecahedron and D4d square
antiprism. . . . . . . . . . . . . . . . . . . . . . . .
The average°(over Molecules A and B) chelate ring bond
distances (A) and their standard deviation of the

mean in Nb(DPM)4 . . . . . . . . . . . . . . . . . . . .

The average (over Molecules A and B) interior angles
of the chelate ring in Nb(DPM)4. . . . . . . . . . . . .

The visible region of the electronic absorption
spectrum of Nb(DPM)4 in dichloromethane (2.83 x 10‘4 M).

The crystal field splitting diagram for the d
orbital energy levels for a D2d dodecahedron and a
D4d square antiprism . . . . . . . . . . . . . . . .

The magnetic circular dichroism spectrum of Nb(DPM)4 . .

The room temperature esr spectrum of Nb(DPM)4 in
hexane O O O I O O I O O O O O O O O O O O O O O O O O O

The esr spectrum (77°K) of Nb(DPM)4 in a hexane glass. .
The room temperature esr spectrum of Nb(DPM)4 powder . .
The esr spectrum of Nb(DPM)4 powder at 77°K. . . . . . .

The powder esr spectrum at 77°K of Nb(DPM)4 doped
in Zr (DPM) 4 O O O O O O O O O O O O O O O O O O O O O O 0

viii

Page

91

93

95

97

100

114

116

121

. 125

129

131

133

139

141

143

I. Statement of Purpose

Although the number of Species exhibiting discrete eight-coordination1
has grown rapidly, the observed stereochemistry is still dominated by two
coordination polyhedra: the square antiprism and dodecahedron.1—4 In
the case of tetrakis chelate complexes, M(chel)4, these two polyhedra
can give rise to nine stereoisomers (Figure 1). Among the various M(che1)4

complexes investigated, only the D antiprism and the DZd’ D2(gggg), and

2
S4 dodecahedron have yet been observed in the solid state. Very little
stereochemical information is available for such complexes in solution.
Previous attempts to deduce their stereochemistry by nmr SpectroscOpy
have been thwarted by their rather remarkable stereochemical lability.5
The initial object of the research was to investigate the reactions
of Nb(V) and Ta(V) pentachlorides and beta-diketones* in solution, with
the hOpe of preparing eight-coordinate M(dik)4+ cations suitable for
stereochemical studies by nmr spectrosc0py. Diketonate ligands were
selected for two important reasons: (1) they are known to form higher
coordination number complexes with transition metal elements to the
left of the periodic table,6 and (2) the terminal R groups on the
ligand provide a convenient means of deducing stereochemistry and
possible isomer distributions by conventional F19 and H1 nmr spectroscopy.
These synthetic studies led to the discovery of several new Ta(V)

+
and Nb(V) complexes, including one possibly containing the M(dik)4 ion.

Despite the positive charge on the ion, which was expected to provide a

 

* A beta-diketonate anion may be represented as (R'COCHCOR)- where R may
be identical to R'. See Appendix A for a list of ligand abbreviations.

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substantial barrier of activation for stereochemical rearrangement yi§_
intramolecular bond-rupture pathways, the lifetime of the complex in its
stereochemical ground state was much too short on the nmr time scale to
obtain the desired information.

A new, stable Nb(IV) complex of the type, Nb(dik)4 was also discovered.
This unusual eight-coordinate d1 metal ion complex was amenable to
characterization by various forms of Spectrosc0py, both in the solid state
and in solution. Therefore, an X-ray structure determination of the
complex was undertaken, and its spectroscopic prOperties in the solid
state and in solution were correlated with its stereochemistry in the

two phases.

II. Survey of Niobium and Tantalum Beta-Diketonate Chemistry

A review of the chemistry of niobium and tantalum beta-diketonates
reveals that a variety of species have been reported. There are two
general classes of complexes for the elements in the +5 oxidation state:

(1) Oxo complexes of the type, [MOX2(dik)]x, [M0X(dik)2]x, and
[MX3(dik)]20, where X - halogen and dik - beta-diketonate ligand.

(2) Mixed alkoxo and/or halo complexes of the type, MX2(OR)2(dik),
M(OR)S_x(dik)x (x 8 1,2, or 3) and MX4(dik).

The +4 oxidation state also exhibits two classes of complexes:

(1) Mixed complexes containing halides of the type, MX4_x(dik)x

where x - 2 or 3.

(2) Tetrakis diketonates, M(dik)4.

5

The first class of the M(V) group includes [NbOC12(acac)]x,7-9

0 DBM]20.11b Rosenheim and Roehrich reported

3
still another oxo complex of the type, NbO(C5H602)33-.12 This complex

[NbOBr (ACAC) le ,1 and [TaCl
was the first example of a Nb beta-diketonate. Hydrated Nb(V) oxide
(niobic acidl3) was allowed to react with a basic solution of acetylacetone
to obtain the salt, K2H[NbO(C5H602)3].1.5(C5H802). The guanidinium

salt, (CN3H6)H2[NbO(CSH602)3], was also prepared. In these compounds the

acetylacetonate anion was formulated as a dinegative Species based on

elemental analyses, but the formulation has yet to be verified.

The compound, [(NbOC12(ACAC))]x, was prepared by the reaction of

NbOCl3 with acetylacetone. The analogous reaction with NbOBr3 yielded
the disubstituted derivative, [NbOBr(ACAC)2]x, which also retained the
Nb—O-Nb linkage. The only Ta example in this class is a dibenzoylmethanate

derivative, [TaCl DBM]20, which was prepared by heating a mixture of TaCl4

3
and HDBM in refluxing acetonitrile for five minutes. It was suggested

that the diketone acts as the oxidizing agent in the reaction. No MO(dik)3

complexes are known with beta-diketonates but the related ligand,
trOpolone does form NbO(Tp)3.l4a’14b
The MX2(OR)2(dik) complexes where M - Nb(V) and Ta(V), X = Cl and
Br, R s CH3 and CZHS’ and dik - ACAC or BZAC, were first prepared by
allowing the metal pentachloride and diketone to react in the apprOpriate
alcohol.15 This synthetic method has been used more recently to prepare
related derivatives with salicylaldehyde, acetoacetanilide,
benzoylacetanilide, 2-hydroxyacetophenone, and o-hydroxybenzophenone in
place of the diketones.16 NbX2(OR)2ACAC can also be prepared from the

10

oxychloride8 and oxybromide of Nb(V) by solvolysis of the Nb-O-Nb

bond with the appr0priate alcohol.

6

The mixed alkoxide-diketonates, M(OR)5_x(dik)x where x = 1,2, and

3, M 8 Nb(V) and Ta(V), R 8 CH3,.£rC H and C H5, and dik = ACAC, BZAC,

4 9 2
and DBM, represent the most extensive series of complexes yet prepared.17-19
Beta-ketoester derivatives have also been prepared.20-22 The ethoxide

and methoxide complexes were isolated from the reaction of the metal
pentalkoxide and corresponding beta-diketone in benzene solution. The
‘57C4H9 derivatives were prepared by metathesis reaction of the ethoxide
complex and tfbutanol in benzene. The methoxy-acetylacetonate derivatives,

MC1(OMe)3ACAC, were prepared from the reaction of M(0Me)4ACAC with

19 b

MC12(OMe)2ACAC. The only example of a Mx4(dik) complex is TaC14(DBM).11

It was isolated from a mixture of TaCla and dibenzoylmethane in acetonitrile.

No complexes of the type, M.Cl(dik)4 are known with beta-diketonates,

14a,14b

but again, trapolone forms both the Nb and Ta derivatives. The Nb

complex was obtained by adding a dichloromethane solution of the ligand

to NbCl5 in dichloromethane and ether. The Ta species was isolated

after heating a mixture of TaCl and trOpolone in refluxing acidic

5

methanol for fifteen minutes.

Examples of Nb(IV) chelates of the type, MX4_x(dik)x are NbC12(DBM)2

lb

and NbCl(Tp)3.1 NbC12(DBM)2 was prepared by heating a mixture of the

free ligand and NbCl in refluxing acetonitrile. As noted above, the

4
analogous reaction with TaCl4 led to oxidation of the metal to give

TaC14(DBM) or [TaCl3(DBM)]20 depending on the reaction time. NbCl('I'p)3

was prepared by heating NbCl and trOpolone in refluxing acetonitrile.

4
Five tetrakis (beta-diketonato)niobium(IV) complexes are known

with ACAC, TTFA, BTFA, BZAC’ and DBM.1la,llb

11a,llb

The tropolone derivative

lb

also exists. The only Ta(IV) species is Ta(DBM)4.1 With the

exception of Nb(ACAC)4, the complexes were prepared from NbCl and the

4
diketone by using triethylamine to help drive the reaction to completion.

Nb(ACAC)4 was prepared by heating a mixture of NbCl and T1(ACAC) in

4
acetonitrile at reflux temperatures for five minutes. When dioxane

was used as the solvent, Nb(ACAC)4°Dioxane was obtained. Two methods were
successful in preparing the TTFA derivative. In the first case,
acetonitrile was the solvent and the reflux time was five minutes. In

the second method, the reflux time was reduced to one minute and the
reaction was conducted in dioxane. The BTFA, BZAC, and DBM chelates

were all similarly prepared with toluene, dioxane, and acetonitrile

used, respectively, as solvents. The reflux times varied from one to

five minutes. The complexes are readily hydrolyzed in solution.

Nb(TTFA)4 and Nb(BTFA)4 in the crystalline state are stable toward
atmospheric oxygen and water. The remaining derivatives, however,

are decomposed by atmospheric oxygen and water at room temperature.

In general, the constitution and structure of the complexes described
above in both the solid and solution state are poorly defined. The
presence of Nb—O-Nb bridging in the polymeric [NbOC12(A.CAC)]x and
[NbOBr(A.CAC)2]x Species has been indicated by strong, broad infrared
bands near 820 cm"1 and 825 cm-1, respectively.10 These frequencies
lie closer to the corresponding Nb—O-Nb vibrational mode observed at

770 cm_1 for NbOCl than to the Nb = 0 stretching modes at 945, 935 cm"1

3
and 910, 890 cm-1 in NbOBr3 and NbOC12(OCZH5)Bipy, respectively.10

A crystal structure of the latter compound has shown it to be
six-coordinate, thus verifying the Nb - 0 formulation.23 [TaC13(DBM)]20
is apparently a discrete oxo-bridged dimer as supported by the presence

of a fairly strong Ta-O-Ta band at 809 cm-l.11b As in the case of the

Nb = 0 stretching frequency, the Ta = 0 stretch exhibits strong doublets
at 935 and 919 cm"1 in TaOC13(Dioxane)2.11b Metal-oxygen (ligand) and
metal-halogen frequencies have also been assigned, but they have not
contributed to additional structural insight.8’9 Powder diffraction data
have been obtained for [NbOClZACAC]x but no new information beyond the

conclusion that the complex is not isomorphous with NbOCl was gained.10

3
Monomeric formulations have been suggested for the members of the
MX2(OR)2(dik), M(OR)5_x(dik)x, and MX4(dik) families. However, possible
solvolysis and/or dissociation in solution leave the question of solution
state stereochemistry unanswered. Ebulloscopic molecular weight studies
of the MX2(OR)2ACAC series in the parent alcohols led Djordjevic, g£_al.,

to suggest that solvolysis may occur to form neutral and ionic species:

ROH
(1) NbX2(OR)2ACAC v—‘A NbX2(OR)3 + 3+ + ACAC-

1/2 Nb2X4(OR)6

ROH
(2) NbX2(OR)2ACAC .—-—‘" NbX(OR)3ACAC + 11+ + x"

II +

Nb(OR)4ACAC + H + x"

Thus, the low molecular weight values observed could represent an
average of the above dissociation products. Acidity of the alcoholic
solutions has been cited as further supporting evidence for the
dissociations. However, conductivity measurements by Syamal, g£_§1.,16
are consistent with a 2:1 electrolyte and suggest the existence of
M(OR)2(HOR)2(dik)2+ ions in solution. Quantitative precipitation of

silver chloride further substantiates halogen dissociation in methanol.

In acetonitrile, the molar conductance values are between those expected

for a 1:1 and a non-electrolyte, implying that the weaker donor solvent
replaces fewer halogen atoms. Vapor pressure osmometric data measured
in both chloroform and benzene solutions16 gave high molecular weight
values which increased as a function of time. This time dependence is
believed to be due to polymerization of the molecule in the less polar
solvents.

Evidence that the MX2(OR)2(dik) complexes undergo diketonate ligand
dissociation and decomposition in solution also exists.16 Optical spectra
in methanol and aged benzene and acetonitrile resemble free ligand
Spectra. The presence of acetone in carbon tetrachloride and methanol
solutions of the complexes has been detected by gas chromatography.

Ligand decomposition is further indicated by nmr spectra of the aged
solutions which resemble neither fresh solution nor free ligand spectra.
Other nmr studies indicate diketone and alkoxide exchange is Slow on the
nmr time scale since the Spectra of the complex and free ligand are
identical to the sum of the component Spectra. Attempts were made to
deduce the stereochemistry of the neutral monomeric molecule in solution
by studying a derivative with an asymmetric diketonate ligand.16 Although
a definitive assignment was not possible, a.£52§§rdichloro arrangement was
favored.

Further investigations of solution state equilibria have been
conducted by titration of Nb(V) and Ta(V) alkoxides in methanol solution.19

2+, M(OR)3ACAC+, and M(0R)4ACAC were found to exist, with the

M(OR)2ACAC
Nb Species being more stable than the Ta analogs. Infrared assignments
have been made for many of the complexes but no Structural information

was deduced.8’9 Powder diffraction data on the MX2(OR)2ACAC system

indicate that the methoxy-chloro and -bromo derivatives are isomorphous,

10

whereas the ethoxy complexes form a separate isomorphous group.8

Aside from ebullosc0pic molecular weight measurements and elemental
analyses, no other meaningful data are available on the M(OR)S_x(dik)x
series. Molecular weights of these oils in benzene indicate monomeric
species. They may be six, seven, and eight-coordinate, reSpectively,

17,18

when x - 1,2, and 3. The Nb derivatives are more volatile than

the Ta analogs. Also, alkoxide ligand exchange is faster in the niobium
complexes than in the tantalum derivatives.17
Very little structural information is available for the two known
Nb(IV) complexes in the NbX4_x(dilc)x Class. A low effective magnetic
moment (0.40 B.M.) at room temperature for NbCI(Tp)3 has been interpreted
in terms of a polymeric structure.11b The value of 1.58 B.M.for NbC12(DBM)2,
however, is typical for Six-coordinate monomeric Nb(IV) complexes.11b
The tetrakis chelates, M(dik)4, are eight-coordinate monomers, with
the possible exception of the tropolone derivatives being polymeric.11b
In the dioxane adduct, Nb(ACAC)4'(Dioxane), the coordination number of
Nb may be nine. This complex exhibits an infrared Spectrum similar to
oxygen-coordinated dioxane complexes, and the visible Spectrum is
Significantly different from Nb(ACAC)4.11b Ultraviolet and visible
spectral data are also reported for the other tetrakis Species and
are interpreted in terms of possible metal d-d transitions, intraligand
singlet to triplet transitions, and charge transfer transitions.11b
Attempts at making a specific stereochemical assignment in this
class of compounds are based on non-documented X-ray powder diffraction
data and Sketchy esr data. Deutscher and Kepert11b report that Nb(TTFA)4
is not isomorphous with M(TTFA)4 where M - Zr, Hf, Th, Ce, U, and Pu,

but the structure of this latter isomorphous series of compounds has not

yet been reported. Nb(DBM)4 is not isomorphous with Th(DBM)4 (a D2d

dodecahedron24), and Nb(ACAC)4 is not isomorphous with Zr(ACAC)4 (a D2
Square antiprism3b). The authors also describe the esr spectra at

room temperature of Nb(ACAC)4 and Nb(DBM)4 as consisting of a broad
asymmetric signal showing the shape predicted for a signal with gi

greater than g' . The values for gl are 1.95 and 1.98, respectively,

 

but gll values were not reported. Thus, on the basis of these data,
they conclude that a dodecahedral, rather than square antiprismatic

stereochemistry, is indicated.

III. EXperimental Section
A. Reagents
The following commercially available reagents were used without
further purification unless otherwise indicated.

(1) Aquasorb, P - Mallinkrodt Analytical Reagent

205

(2) Chlorine gas, Cl - Matheson Co.

2

(3) Cupric Acetate, Cu02H302 - Fischer Scientific Reagent

(4) ‘Methyl pivalate, C6H1202 - Aldrich Chemical Company

(5) Niobium pentachloride, NbCl
Chemicals, 99.52

5 - Research Organic/Inorganic

(6) Niobium shot, Nb - Alfa Organics, m2n8—t2n7

(7) Pinacolone, C6H120 - Aldrich Chemical Company

(8) Sodium amide, NaNH - K and K Laboratories

2

(9) 2,2,6,6-tetramethy1-3,5-heptanedione,
Chemicals

C11H2002-Eastman

(10) Triethylamine, (CZHS)3N - Eastman Chemicals

(ll) Tetramethylsilane, (CH3)ASi - Aldrich Chemical Company

11

12

B. General Techniques Used in the Reactions of Metal Halides
In view of the air sensitivity of the Nb and Ta halides and
of most of the products they form upon reaction with beta-diketones,
Special procedures were necessary to maintain anhydrous conditions in
the preparative reactions. A11 glassware contained sidearm stopcocks
to allow entry of dry nitrogen or argon gas. This included erlenmeyer
and round bottom flasks, filter frits, and dropping funnels. Prior to
use,the apparatus was cleaned in a ROM - EtOH bath (except for fritted
glassware) followed by a soaking in a KZCrZO7 - H2304 bath and rinsing
with distilled water. After drying for at least 24 hrs. at £3, 180°C,

the glassware was cooled in a CaCl desiccator and flushed with dry

2
nitrogen. It was then transferred to a nitrogen-filled glove bag
(obtained from Instruments for Research and Industry, Model X-l7-l7)

which contained a beaker of Aquasorb to help maintain a dry atmosphere.
All transfers of hygroscOpic reagents were performed in the glove bag,
although in a few cases, a dry box was used.

Most reactions were conducted in a small erlenmeyer flask (50-250 ml)
equipped with a gas inlet tube to admit dry nitrogen. A gentle flow of
dry nitrogen or argon served to both insure anhydrous reaction conditions
and to help remove product gases (e.g. HCl) that formed during the
reaction.

To filter the reaction mixture, a medium porosity (10-20 u) sidearm
filter frit, attached to a sidearm erlenmeyer receiving flask, was
attached to the reaction flask. The sidearm stapcock on the filter frit

enabled a flow of nitrogen to be passed through the frit as well as the

reaction flask while the apparatus was being assembled (see Figure 2).

13

.xmmaw wafl>fimooula .mpwmaH
non wcauufium uwuoawma suaa uwum nouafim zuamouoa
Ensues oq\q~ mlo .uaHOH onmeImHmEom oq\em mum
.uco>aom nmma Lugs Henson mafiaaouml< ANV mxmmaw

wca>fioomu|o .uaum nouflfim muamouoa enemas oq\¢~ mum
.xmmam coauomou Hmafiwfiu01< Aav "mommnuawm wafiusw
macausaom msouvmnam wcaavcm: wow mHnEommm woumumao<

.N muswfim

 

 

l4

 

 

 

 

Figure 2

15

DevelOpment of excessive pressure was avoided by use of a mineral
oil-filled nitrogen bubbling tower included in the nitrogen line. Once
the filtration apparatus was inverted, rapid filtration could be assured
by either passing nitrogen into the reaction flask through the sidearm
and/or attaching a periodic vacuum to the sidearm of the receiving flask.

Washing of the solid residue was accomplished by replacing the
reaction flask with a drapping funnel containing the apprOpriate amount
of nitrogen-flushed wash solvent. The solvent was flushed at least
fifteen minutes before use. The wash solvent was flushed through the
frit in a manner analogous to the filtration procedure by using the
three-way stopcock on the drapping funnel to attach the nitrogen line.
After the washing was complete, the drapping funnel and receiving flask
were replaced by adapters (see Figure 2) and the product was dried
$2 2&222-

Recrystallization of the product was conducted in a Similar manner.
The recrystallizing solvent or solvent mixture was added by means of the
drapping funnel to the solid residue contained in the filter frit. Heat
was applied, as necessary, with the aid of a heat gun while the desired
product solution was being flushed into the receiving flask with nitrogen.
An alternative method of recrystallization involved transferring a
pre-weighed portion of the crude product to a sidearm erlenmeyer and
adding the appropriate solvent(s) in the glove bag. The mixture was
heated and Stirred magnetically while passing nitrogen over the solution
surface. Filtration was achieved as in the original filtration process,
and the flask was set aside in the refrigerator or at room temperature,

as desired.

16

All solvents were dried at least several days and usually, several
weeks, over drying agents prior to use. Calcium hydride was used to
dry dichloromethane, chloroform, acetonitrile and carbon tetrachloride.
Molecular sieves were used to dry nitrobenzene, which was pre-purified
according to the procedure outlined by Taylor and Kraus.25 Triethylamine
was freshly-distilled over barium sulfate at 84°C. All other solvents
were refluxed over lithium aluminum hydride.

C. Purification of Niobium Pentachloride

Niobium pentachloride was purified by sublimation iguygggg.

A pre-dried pyrex glass tube, equipped with a ground glass joint and

vacuum stapcock, was loaded with 6-8 grams of yellow NbCl powder in a

5
dry box. It was Slowly evacuated and placed into a tube furnace so that

the end containing the NbCl was near the middle of the heating coils.

5
A small piece of aluminum foil wrapped around the end of the tube kept
an iron-constantan thermocouple in place. The furnace was placed on an
incline (93, 30°) with the loaded end of the tube slanting downward. The
temperature was Slowly increased over a three day period to 125°C. The
first trace of sublimate was visible after approximately 24 hours and a
temperature of 64°C. A very crystalline (plate-like prisms and feathery,
needle-like networks) yellow product had sublimed into the cold end of
the tube after three days. The reaction tube was dismantled in a dry
box, and the product was scraped out with the aid of a bent spatula.
Tantalum pentachloride was sublimed in an analogous manner.
D. Syntheses
1. Preparation of:giobiumgtggrachloride.
NbCl was prepared by reaction of Nb and NbCl at elevated

4 5

temperatures:26

Nb + 4NbC15 8 5NbC14

17
Freshly-sublimed NbCl5 (27.6 g, 0.102 moles) and niobium shot (2.37 g,
0.0256 moles) were loaded into a dry 45 cm (30 mm o.d.) pyrex tube in a
dry box. The tube was evacuated to a pressure of 10‘5 torr and carefully
sealed with a flame. The tube was placed into a two-zone tube furnace
with the temperature of each 30 cm zone individually controlled by
Variacs. The entire tube was wrapped in aluminum foil to help secure
the two iron constantan thermocouples and help improve the uniformity
of the temperature gradient along the reaction tube. The zone containing
the loaded end of the tube was warmed to 70° before activating the
second zone. The temperature of the loaded end was then increased to
400-410° while increasing the temperature of the second zone to 250-260°.
After a reaction time of five days, a Special shutdown procedure was
followed. During the cooling period, the temperature of the "hot" zone
was kept approximately 50°C above the "cool" zone to prevent dispropor-
tionation of the product. Approximately 23 grams of a dark purple,
finely-crystalline product was obtained in the "cool" zone. The NbCl4
was purified by sublimation iggygggg_at 150°. Approximately 2 days were
required to complete the sublimation. The product was placed in a
Schlenk tube and Stored in a dry box.
2. Preparation of 2,2,6,6-tetramethy1-3.S-heptanedione.
The synthesis was patterned after the method reported by Adams

and Hauser.27 The following reactions are used in the synthesis:

+NH

CH coc<cn + NaNH 1 Na+[CH2COC(CH3)3]- 3

3 3)3 2
pinacolone I

18

1 + (CH3)3CCOOCH3 z Na+[(CH3)BCCOCHCOC(CH3)3]- + CH30H
methyl pivalate II
H20
11 1+ (CH3)3CCOCH2COC (C113)3
dipivaloylmethane
(HDPM)

A solution of pinacolone (225 ml, 1.8 moles) in 270 m1 of diethyl ether
was added drOpwise, with stirring, to a grey suspension of sodium amide
(70.2 g, 1.8 moles) in 1500 ml of diethyl ether. The addition was
completed in about 1 1/2 hours. Methyl pivalate (235 ml, 1.8 moles) in
23, 20 m1 of ether was then added to the greyiSh-green suspension over a
30 minute period. The mixture was heated at reflux temperature overnight.
The reaction mixture then was cooled to room temperature and carefully
poured into a 4 liter beaker containing‘gg. 1500 ml of water. Approximately
600 m1 of 6N_HC1 was added to adjust the pH to 7.0 (as indicated with
Hydrion paper). The aqueous and ethereal layers were separated, and the
water layer was extracted eleven times with 200 m1 portions of ether.

The following color changes were observed in the ether and water layers

before and after neutralization:

 

 

 

 

 

ETHER LAYER = orange HCl g_ orange-yellow
H20 LAYER " greenish-brown ' grayish-green
pH7 A_‘ bright yellow during extraction )_ orange
' grayish-green " pale yellow
final extraction ‘ colorless

 

 

light yellow

19
The ether solutions were combined (23: 3700 ml) and evaporated on a
Steam bath until boiling ceased. Approximately 350 m1 of orange liquid
product remained. To this product was added a solution of cupric acetate
(120 g, 0.600 mole) in 350 m1 of methanol and 1050 ml of water. The
conversion of the ligand to the copper salt was necessary to isolate a
product of higher purity i.e., without accompanying Side products of the
initial acylation reaction. After heating the copper salt solution to
near boiling, it was quickly filtered through a hot thhner funnel to
remove any undissolved cupric acetate. During the heating process the
color of the solution changed from orange to dark green. Cooling the
solution to room temperature afforded dark purple crystals of c0pper(II)
dipivaloylmethanate, which were collected by filtration. The compound
was recrystallized from 1700 m1 of hexane which resulted in a yield of
110 g (28.42).

The copper salt was divided into three equal portions, and each .
portion was treated in the following manner. The crystals were dissolved
in 500 ml of ether, and the solution was shaken in a separatory funnel
with one liter of 102 sulfuric acid. The layers were separated, and the
blue aqueous layer was wahhed twice with 100 ml of ether. The yellow
ethereal solutions obtained by treating the three portions of Cu(DPM)2
were combined and evaporated on a steam bath until boiling ceased. The
remaining dipivaloylmethanate was dried over 20 g of anhydrous sodium
sulfate for 3 hours and then was transferred to a distilling flask. The
product was fractionally-distilled through an insulated vigreaux column
under dry nitrogen at a pressure of 20 torr. Three fractions boiling in
the following ranges were collected: 80-93.5°; 93.5-96°; 96-97°. The

first two fractions exhibited the expected tertiary butyl proton

20
resonance at T8.85 and methylene proton resonance at T4.23 in the nmr
spectrum. However, impurities were also present as indicated by a weak
set of multiplets between T7.66 and 18.16, and a strong, sharp resonance
at 18.80. Thus the first two fractions were discarded. The third
fraction Showed no impurities in the nmr spectrum. The yield was 90 ml
(272, lit.27 28%).

3. Preparation of Dipivaloylmethanato Tantalum(V) Tetrachloride.

 

Dipivaloylmethane (22.2 ml, 120 mmoles) was added at room
temperature to TaClS (8.63 g, 24.1 mmoles) to form immediately a yellow
suspension. The yellow suspension was stirred for 30 minutes, and a
vacuum was applied to remove the by-product HCl. After filtration of
the mixture, the yellow solid (3.40 g) was washed with hexane and dried
i2_y§ggg_for 6 hours. To facilitate the removal of any insoluble
impurities and occluded free ligand, the compound was dissolved in
dichloromethane, and the solution was filtered and pumped to dryness.
The bright yellow solid was dried in_ya£ug_at room temperature for
15 hours and then at 80° for 3 hours; m.p. 123-128°. The yield was
3.40 g (282).

Anal. Calc'd. for Ta(C )Cl4: C, 26.10; H, 3.78; C1, 28.05;

11H19°2
Ta, 35.74. Found: C, 25.87; H, 3.86; CI, 25.22; Ta, 36.07.

The filtrate of the above compound which had become cloudy after
aging for £3, 1 hour was filtered, and a bright yellow solid was
obtained. It was dried in_y§gug at room temperature for 4 hours.
M.P. 190-215° (with decomposition).

4. Preparation of Bis(dipivaloylmethanato)tantalum(V) Trichloride.

Dipivaloylmethane (10 ml, 54 mmoles) was added to TaCl5 (3.90 g,

10.9 mmoles) as in the preparation of TaDPMCl The reaction mixture

4.

21
was stirred for 30 minutes and then heated on a steam bath for 1 1/2 hours.
After additional stirring at room temperature for 12 hours, hexane was
added to the solution. A pale yellow precipitate formed which was
filtered and dried in yaggg_for 1 hour. The crude product was washed
with hot hexane, recrystallized from dichloromethane-benzene, and dried
in_yaggg_for 12 hours at 80°; m.p. 268-27l°, (with decomposition). The
yield was 1.76 g (25%).

Anal. Calc'd. for Ta(C O ) Cl ° C, 40.41; H, 5.86;

11H19 2 2 3'
Ta, 27.67; mol. wt., 659. Found: C, 40.22; H, 5.88; Ta, 27.22;

-3 0
mol. wt. (C6H5N02), 644, II (1.08 x 10 MLin C6H5N02 at 25 ),
l 3

12.4 ohm-1cm2mole- ; II (0.33 x 10- M_in CHBNO2 at 25°), 54 ohm-1cm2mole—l.

After aging for £2 24 hours, the filtrate of the above compound
produced a crop of yellow crystals which were filtered. They were
recrystallized in dichloromethane—diethylether and analyzed. The
mother liquor of the above filtration also continued to produce more
crystals upon aging.

‘Anal. (first crop): C, 37.05; H, 5.22; C1, 15.81.

5. Preparation of Dipivaloylmethanatoniobium(V) Tetrachloride.

A solution of dipivaloylmethane (0.91 ml, 4.95 mmoles) in

20 ml dichloromethane was added dropwise, with stirring, to NbCl5
(1.21 g, 4.50 mmoles). An immediate reaction was indicated by vigorous
frothing and the formation of an orange solution. A vacuum was applied
during a 30 minute stirring period, after which, 30 m1 of hexane was
added. After further stirring for 20 minutes the orange reaction

mixture was filtered. The orange solid residue (0.27 g) was washed with

hexane and dried in_vacuo for 1 1/2 hours; m.p. 167°, (with decomposition).

22
The red-orange filtrate became cloudy after addition of 60 m1 of
hexane, and a precipitate began to form after removal of 30 m1 of
solvent by evaporation under a Stream of dry nitrogen. The finely-
divided red-orange precipitate was filtered and dried in_yagug for
2 hours; m.p. 139-142°. The yield was 1.09 g (59%).

Anal. Calc'd. for Nb(C )014: C, 31.61; H, 4.58; C1, 33.93;

11H19°2
Nb, 22.23. Found: C, 31.76; H, 4.98; Cl, 29.48; Nb, 22.68.

6. Preparation of Bis(dipivaloylmethanato)niobium(V) Trichloride.

A solution of dipivaloylmethane (8.7 m1, 47.4 mmoles) in 35 ml

of dichloromethane was added to NbCl5 (2.56 g, 9.49 mmoles), and the
orange reaction mixture was stirred for 3 hours. During this time a
vacuum was applied to remove the HCl. After an initial reaction time
of 40 minutes the color of the solution changed from clear orange to
opaque red—orange. An orange precipitate began to form after 50 m1 of
hexane was added to the mixture. The mixture was allowed to age for
one hour while the volume was reduced by a gentle Stream of dry nitrogen.
The orange precipitate was filtered and dried in yaggg_for 3 hours.

The filtrate was allowed to age for 24 hours and was filtered
again to remove some crystals that had formed. The new filtrate was
allowed to age for one week. During this time a mixture of orange
needle-like and prismatic crystals had formed. The mother liquor was
decanted and the crystals were dried with a Stream of dry nitrogen for
3 hours3m.p. 139-144°. The yield was 0.85 g (15%).

Anal. Calc'd. for Nb(C C, 46.70; H, 6.77;

11“19°2’2013‘
c1, 18.80; Nb, 16.42. Found: c, 46.96; a, 6.94; c1, 14.26;

Nb, 17.86.

23

7. Preparation of tetrakis(2,2,6,6-tetramethyl-3,S—heptanedionat02—
niobiumfiIV).

An acetonitrile solution of dipivaloylmethane (39.5 ml,
214 mmoles) containing triethylamine (11.2 ml, 80.3 mmoles) was added
drapwise, with stirring to an acetonitrile suspension of NbCl4 (4.51 g,
192 mmoles). After 2 days the blue-black suspension was filtered and a
similarly-colored solid was obtained. The product was washed through
a filter frit with hexane, leaving behind a grayish-white solid (triethyl-
aminehydrochloride) and resulting in an Opaque purple filtrate. The
filtrate was evaporated under vacuum at room temperature, and the finely-
crystalline dark purple residue was dried ipdgpgpp.at room temperature
for 5 hours; m.p. 219-233°. The yield was 7.13 g (532).

Anal. Calc'd. for Nb(C C, 63.98; H, 9.27; Nb, 11.25;

11H19°2)4‘
mol. wt. 826. Found: C, 63.86; H, 9.23; Nb, 11.46; mol. wt. (C6H5N02),

777; A(2.93 x 10-3.M.in CH2C12 at 26°), 0.0901 ohm-1cm2mole-1;

A(1.11 x 10_4‘M_in C6H5NO2 at 26°), 6.88 ohm-1cm2mole—1;

2.1 B.M.; ueff(Faraday), 1.9 B.M.

ueff(Evans),

8. Preparation of oxodichlorodipivaloylmethapatoniobium(Vz.

 

Anhydrous oxygen-free chlorine (8.94 mmoles) dissolved in
200 m1 carbon tetrachloride was added in four-50 m1 portions to a carbon
tetrachloride solution of Nb(DPM)4 (2.51 g, 3.04 mmoles). After each
successive addition, the solution changed color from the initial deep
purple to blue-green and finally to yellow when the fourth portion of
chlorine was added. The diamagnetic yellow solution was evaporated 12
ypppp to yield a brown 011. Addition of hexane resulted in the formation
of a golden yellow precipitate which was filtered and dried ipflggppp,

at room temperature for 3 hours. The compound decomposes to a black

24

solid at 280°. The yield was 0.35 g (322).
Apgl. Calc'd. for NbC11H1903C12: C, 36.39; H, 5.28; C1, 19.53;
Nb, 25.59. Found: C, 36.61; H, 5.32; Cl, 19.41; Nb, 25.36.
E. Physical Methods of Characterization
1. Elemental Analysis
Elemental analyses were performed by Galbraith Laboratories,
Knoxville, Tennessee. Niobium was determined by atomic absorption.
2. MeltipgfiPoipp
Melting points were determined with a Thomas-Hoover 6406-H
capillary melting point apparatus. Capillaries were sealed with a plug
of plasticene to avoid hydrolysis or oxidation of compounds during the
determination of melting points.
3. Molegplar Weight
Molecular weights were determined cryoscOpically in nitro—
benzene or benzene. The apparatus was equipped with a S 19/38 Beckman
thermometer graduated at 0.01°C intervals. An attached magnifying reader
made possible readings estimated to 1;0.001°C.
The molal freezing point depression constants (Rf) were determined
with recrystallized benzil as the reference solute. The freezing
depressions were measured in the concentration range of pp, 0.005 p_to

0601 E.

4. Molar Conductance
Conductance measurements on the Ta(V) complexes were made
with a Beckman Model -RC-16B2 bridge, whereas the Nb(IV) complexes were
measured with a WSyne Kerr Model B221 Universal Bridge. Two Freas type

conductivity cells with bright platinum electrodes were used. The cell

25
constants, determined with a standard KCl solution, were 0.2139 cm.-1
and 0.1941 cm-l. Solution concentrations in nitrobenzene, dichloromethane
and nitromethane ranged from §_a_. 0.0003 _M_ to 0.07 M.

5. Mpgnetic Susceptibility

(a) Evans Method28 - Dichloromethane solutions were

measured into an nmr tube assembly as shown in Figure 3. The nmr Spectra
were obtained with a Varian 56/60-D high resolution Spectrometer operated
at 60 MHz. Both CH2C12 and TMS resonances were measured to obtain the

paramagnetic shift. The following equation was used to calculate XM’

the molar magnetic susceptibility:

= 3Av MW
XM 2nvC
where Av = paramagnetic Shift or frequency

separation, in Hz, of either TMS or

dichloromethane,
MW = molecular weight of solute,

v - frequency of nmr Spectrometer
(60 x 106Hz),

and C = concentration of solute in g/ml.

(b) Faraday Method - Measurements were made with an Alpha Magnetic
Susceptibility System equipped with a Model 3002-1 current regulated
power supply, a Model 3022 vacuum controller, and a Model 4600 4 inch
adjustable electromagnet. The field strength of the magnet at 30 amps
and a one inch gap was 11,300 Gauss. A quartz bucket, which was used as
the sample holder, was calibrated with Hg[Co(CNS)4]. Readings were

taken at 500.0 and 800.0 amps to an accuracy of 3 0.00003 g. Sample

26

Figure 3. NMR tube assembly for Evans
magnetic susceptibility measurement.

27

‘ ............... Pressure COP

.......... . . Tef'on tape

\.\

 

.. ................... TMS+ solvent

- - TMS +solvent+solute

 

 

Figure 3

28
weights were approximately 20 mg. Diamagnetic corrections for the
ligand29 and niobium atom30 were applied. In a typical Faraday experiment,

the observed XM° was 690 x 10-6 cgs units, and the diamagnetic correction

term was 720 x 10”6 ch units. The following formula was used to calcu-

late XM’ the molar magnetic susceptibility:
a a+§F'
xM (W x 106) MW
where o = correction for displaced air (assumed negligible),
8 = calibration constant which corrects for suscepti-
bility of sample holder,
F' = F - 6
where F = change in weight of the sample holder plus the
sample when the field is applied,
6 = change in weight of the empty sample holder when
the field is applied,
W = weight of sample in grams,
and MW = molecular weight of the sample.

6. Infrared Spectra

Infrared Spectra were obtained with a Perkin-Elmer 237B
grating infrared spectrophotometer (4000-600 cm-l) and a Perkin-Elmer
457 grating infrared SpectrOphotometer (4000-250 cm-1). The samples
were prepared in a glove bag as Nujol mulls on CSI plates or as

dichloromethane solutions in C31 cells of 0.1 mm pathlength.

29
7. Ultraviolet and Visible Spectra
UV-Vis Spectra were obtained with a Unicam SP. 8008
ultraviolet SpectrOphotometer and a Cary 14 recording SpectrOphotometer.
Dichloromethane solutions prepared in a glove bag were measured in the
concentration range of 9.5.1.- 0.0003 M to 0.001 M. In addition, electronic
absorption spectra in the solid state were obtained from nujol mulls
diapersed on filter paper.
8. Nuclear Magnetic Resonance Spectra
Proton nmr spectra were obtained with a Varian 56/60-D
high resolution Spectrometer Operated at 60 MHz. Chemical shifts were
measured by using tetramethylsilane as an internal standard. All
samples were prepared in a glove bag. Temperatures were determined
from the chemical shift differences between the proton resonances of
methanol.
9. Electrop_Spip_ResonanggfSpgpppp
ESR Spectra were obtained with a Varian E-4 spectrometer
Operated between 9.2 and 9.5 GHz.* Spectra were recorded at room
temperature and at 77°K, the latter temperature made possible by inser-
tion of a liquid nitrogen dewar into the probe. Samples were prepared in
a glove bag by using pre-dried 3 mm quartz tubes which had been alternately
evacuated and flushed with purified nitrogen. After a preliminary seal
with StOpcock grease, the sample tube was removed from the glove bag

and carefully sealed in a flame.

 

* ESR Spectra of Nb(DPM)4 in CH2012 at room temperature and 77° K were
duplicated by Dr. R. D. Bereman, State University of Buffalo. An
X—band Varian 4502-19 linear field Spectrometer was used.

 

30
10. 3:39! Powder Diffracgipp

X—ray powder patterns were obtained with a Debye-Scherrer
and Guinier camera using Cu-Ka radiation. Finely-powdered samples were
loaded into 0.3 mm capillaries for the Debye-Scherrer experiments. In
the Guinier experiments, crushed samples containing a trace of powdered
Platinum as a reference were placed on sample discs containing a strip
of tranSparent cellophane tape on the back side. X-ray d—spacings
were determined from the exposed films with the aid of a Picker x—ray
film viewer.

11. Single Crystal X—Ray Structure Determinatiqp_

Many of the details of the theory and techniques used in
the Single crystal structure determination of Nb(DPM)4 have been presented
in several texts.31-33 Only the general procedures used in the study
are described here.

Air-stable, dark purple needles of Nb(DPM)4 were recrystallized
from a benzene-acetonitrile mixture. Two crystals were necessary to
collect a complete set of intensity data due to decay of the initial
crystal.

The compound was found to possess Laue symmetry m, from oscillation,
equi-inclination Weissenberg, and precession photographic techniques.
Systematic absences of the type, hOR, l = (2n+1), were found and the
Space group was identified as Pc with 4 molecules in the unit cell and
2 molecules per asymmetric unit. The density, as determined by the
floatation technique in ethylene bromide-acetonitrile, is 1.12 g-cm-3.
The calculated density iS 1.12 g-cm_3 based on the cell dimensions of:

a =- 22.30 i 0.05, b = 11.86 i 0.02, c = 19.58 :t 0.05 K, and

31
B = 107.46 :_0.05°. A complete set of intensity data was collected to
a d-spacing of 1.0 A (20 a 100°) using Cu Ra radiation on a Picker Four
Circle Automatic X-Ray Diffractometer controlled by a DEC 4K PDP-8
computer. The "wandering" w step scan procedure,34 with balanced Ni-Co
filters, was used to obtain 3667 independent, observable reflections
(total data merged from 2 sets correSponding to the 2 crystals measured).
Absorption, decay, and Lorentz-polarization corrections were applied to
the intensities to convert them to F 2 values on a relative scale.
The Nb positions were derived from a sharpened three dimensional
Patterson synthesis, and the remaining atoms were located subsequently by
using Fourier methods. The Patterson and Fourier syntheses were performed
with the "Two-and Three-Dimensional Crystallographic Fourier Summation
Program" written by J. Cvildys at the Argonne National Laboratory and
least squares refinement was accomplished with the "ANLFLS, a FORTRAN
Crystallographic Least-Square Program" also written by J. Cvildys. Both
programs were versions modified by R. L. Vandlen of MSU. Best least
squares plane calculations were performed with a "Program B-125 (3600F)
Least Squares Plane and Line Fitter" written at the Argonne National
Laboratory. Bond distances and angles were calculated with the DISTAN
program written by Dr. R. L. Bodner at Michigan State University. All

computer computations were performed on the CDC 6500 at Michigan State

El, Fo — F0 .1

2 F0
by the full matrix least squares refinement with unit weights for all

University. The R factor.R - , was reduced to 0.086

atoms and anisotrOpic thermal parameters for the Nb and oxygen atoms.

IV. Results and Discussion
A. Tantalum(V) and Niobium(V) Derivatives of Dipivaloylmethane

1. Produgts Obtained FrOm the Reaction of TaClg_and H(DPM).

. I . r

 

In an effort to prepare an eight-coordinate Ta(V) complex
with H(DPM), reactions of the metal pentachloride with the ligand were
investigated. The choice of H(DPM) as the ligand was dictated by the
greater degree of solubility imparted to chelates of this ligand than to
chelates of other beta-diketones. Reaction products were typically
yellow powders that were qualitatively characterized by their melting
points, infrared spectra and nmr spectra. The compounds were readily
hydrolyzable in both the solid state and in solution. In many cases,
even under anhydrous conditions, decomposition to free ligand and other
by-products occurred as solutions were aged. Because of these factors,
reproducibility of results was a major challenge in this area of investi-
gation.

A product with a chemical composition approximately corresponding

to the empirical formula Ta(DPM)Cl4 was obtained as a precipitate

 

from the reaction of the anhydrous chloride and neat H(DPM) at a 1 to 5
molar ratio after a reaction time of 30 minutes at room temperature. The
product is a bright yellow powder which is readily soluble in dichloro-
methane. Upon exposure to air for several hours, the compound hydrolyzes,
as indicated by the evolution of HCl gas, to a white insoluble powder.

The white solid shows no DPM ligand absorptions in the infrared spectrum.
A white insoluble precipitate also forms when a dichloromethane solution
of the compound is exposed to air for several hours. Although no elemen-
tal analysis was obtained for the hydrolysis product, it is postulated

to be a tantalum oxychloride.

32

33
The elemental analysis of Ta(DPM)C14, which is presented in Table I
shows an appreciable negative deviation for chlorine. The possibility
of contamination by Oxo-complexes with a Ta-O—Ta or Ta=0 formulation
as described in Section 11 above (p.7) is unlikely because presence
of an oxo-complex should cause a concomitant increase in the carbon
content. Negative deviations of greater than 9% for chlorine analyses

16 for the series of mixed

have also been reported by Syamal, ££_§1.,
chloroalkoxy-diketonates of Ta(V) and Nb(V) described in Section 11
above (p.8). The authors note that the negative deviations increased
as the period of time that the complexes were subjected to a vacuum
increased. No attempt was made to correlate drying time ip_gggpp_to
chlorine content in the case of the DPM derivatives discussed here.
However, it should be noted that the mixed alkoxy complexes were isolated
by rotary evaporation whereas the DPM complexes were filtered and dried
as solids ip_!pgpp. A possible cause for the low chlorine analyses
may be due to erroneous chlorine analyses. The same sample of Ta(DPM)Cl4
that analyzed for 25.22% chlorine (Galbraith) was also analyzed for
12.85% chlorine by the Spang Microanalytical Laboratory (Ann Arbor,
Michigan). In addition, the same sample of Nb(DPM)C14 that was analyzed
for 29.48% chlorine by Crobaugh Laboratories (Cleveland, Ohio) was
analyzed for 12.9 and 13.0% chlorine by Coors Laboratories (Golden,
Colorado).

The solid state infrared spectrum of Ta(DPM)C14 is Shown in
Figure 4. The bands at 1576 and 1562 cm-1 are assigned to the carbonyl

stretching mode. This is well below the free ligand carbonyl bands

which are observed above 1600 cm.1 and shows that the DPM molecule is

34
Table I

Chemical Analyses for Products Obtained from
the Reactions of TaC15 and NbC15
with Dipivaloylmethane

 

Compound %C . p %H <_v %Cl %M
TaCDPM)Cl4 25.87 a .3.86 25.22 36.07
(26.10)—- (3.78) (28.05) (35.74)
Ta(DPIM)2C13 40.22 5.88 ----- 27.22
(40.41) (5.86) (16.27) (27.67)
Nb(DPM)C14 31.76 4.98 29.48 22.68
(31.61) (4.58) (33.93) (22.23)
Nb(DPM)2C13 46.96 6.94 14.26 17.86
(46.70) (6.77) (18.80) (16.42)

 

a
-Va1ues in parentheses are calculated values.

35

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37

acting as a bidentate ligand. No evidence is present in the spectrum
at 900 and 800 cm"1 for a Ta - 0 or Ta—O-Ta formulation, respectively
(see Section II), and a strong broad band at 350 cm”1 is assigned to
overlapping Ta-Cl and Ta—O‘modes.9’35’36

The behavior of Ta(DPM)Cl4 in solution under anhydrous conditions
was investigated by means of nmr spectroscopy. The nmr spectrum of the
compound in dichloromethane is shown in Figure 5. The resonances at
T 8.72 and T 3.43 are due to the Efbutyl and gamma protons of the ligand,
respectively. No decomposition products were observed after the solu-
tion was allowed to age 4 days.

A second product was isolated from the 1:5 TaCl to H(DPM) reaction

5
mixture by allowing the mother liquor to age at room temperature for

one hour. This product was not analyzed, but its proton nmr spectrum
(Figure 6) contained several interesting features. In addition to
resonance lines at T 8.72 and 3.43 which are characteristic of Ta(DPM)C14,
a much more intense set of lines is observed at T 8.84 and 3.80. Closer
.examination of the Efbutyl region at a 50 cycle sweepwidth reveals the
presence of a shoulder at r 8.85 which is probably due to the presence

of free ligand. The gamma proton resonance of the free ligand which
should appear at T 4.23 is too weak to be Observed. After the solution
ages two days, the free ligand resonances have grown and the gamma

proton resonance at T 4.23 is clearly visible. The presence of the new
peaks at T 8.84 and 3.80 in the initial nmr spectrum is apparently due

to a product consistent with a higher degree of ligand substitution,

Since the position of the peaks coincides with the resonances of the

Ta(DPM)2C13 complex to be discussed below. This result is not surprising

38

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42
since the mother liquor contains mainly free ligand. Furthermore, a
correlation exists between the reaction time and the intensity of the
T 8.84 line in the crystallized product. For a reaction time of 24 hours,
the nmr spectrum of the product shows only a trace of the low field
Efbutyl resonance at T 8.72. The product crystallized from the mother
liquor after it had aged £3. 1 day reveals only a high field resonance
at r 8.84.

In view of the probable existence of a higher substitution product
in the 1:5 TaClSIx>H(DPM) reaction mixture, the reaction was repeated
at 100° in order to obtain higher yields of the compound. The carbon,
hydrogen, and tantalum analyses (see Table I) are in agreement with

the formulation Ta(DPM)2C1 The product is a pale yellow powder

3.
and exhibits a greater degree of solubility in dichloromethane than
Ta(DPM)C14. This is consistent with a higher degree of substitution on
the metal atom. As in the case of Ta(DPM)C14, the compound forms a
white powder upon its exposure in the solid state or in solution to
atmospheric moisture.

The molar conductivity at 26° of Ta(DPM)2Cl3 is 54 ohmmlcmzmoleu1
in nitromethane at a concentration of 3.30 x 10"4 M and 12.4 ohmmlcmzmole-1
in nitrobenzene at a concentration of 1.08 x 10”3 M, The 1:1 electrolyte
tetraethylammonium iodide exhibits a molar conductivity of

97 ohm-1cm2mole-1

5 x IO-A‘M,37 The electrolyte [Ti(acac)3)][SbCl6] in nitrobenzene is

at 20° in nitromethane at a concentration of

reported to have a molar conductance of 26.2 ohmmlcmzmole'.1 at infinite

dilution.5 Thus Ta(DPM)2Cl appears to be pg, 50% dissociated in

3

nitrobenzene and nitromethane. This should be regarded as a minimum

43
value, Since independent evidence suggests that the compound undergoes
decomposition upon aging in solution at room temperature (see below).
AS the decomposition proceeds, the conductivity.decreases. For example,

after the solution of TaCDPM)2C1 in nitromethane had aged for 5 days, the

3
molar conductance decreased from 54 to 16 ohm-1cm2mole-1.

In nitrobenzene solution, the molecular weight of Ta(DPM)2C13
corresponds to that expected for a monomer. However, the freezing point
depression of the nitrobenzene solution decreased as a function of time.
This is consistent with a decrease in the number of dissociated species
in solution as decomposition proceeds.

The following equilibrium is suggested to account for the conducti-

vity and molecular weight data:

2 Ta(DPM)2C1 : Ta(DPM)4+ + "16016

3

Heckley and Holah38 have reported complexes of the type, M(dtc)2X3,

where M is Ta(V) and Nb(V), X is C1 and Br and dtc is the N,N-diethyl-
dithiocarbamate anion. The authors state that on the basis of preliminary
conductivity, infrared, and nmr data, the compounds are probably ionic

and could possibly be formulated as [M(dtc)4][MX6]. No conductivity or
nmr data were reported but a strong band at 320 cm_1 was assigned to the
Ta-Cl stretching mode. Other examples of previously reported eight-
coordinate cations of the type M(chel)4+ are reported by Muetterties and
Wright.39 The ligand, tropolone, was found to form this cation with

both Nb(V) and Ta(V). Although another equilibrium involving the

dissociation of a chloride ion to form a six-coordinate cation,

Ta(DPM)2C1£+, may also be present, there is no evidence in the

44
literature for the existence of such a cation for beta-diketonate
ligands.

The solid State infrared spectrum of Ta(DPM)2C13 is Shown in
Figure 7. Complete chelation is again indicated by carbonyl stretching
bands at 1578 and 1568 cm-1. A Strong broad absorption, at 338 cm-1,
similar to the band in the Ta(DPM)C14 spectrum (see Figure 4), is again
assigned to Ta-O and Ta-Cl stretching modes. Earlier infrared studies
of a series of hexachlorotantalate salts have led to the assignment of
a strong, broad absorption with maxima ranging from 307 to 333 cm.1 to

40,41

the v Ta-Cl stretching mode. The shift of the Ta-Cl band from

3

350 cm"1 for Ta(DPM)Cl4 to 338 cm.1 for Ta(DPM)2C1 brings the absorption

3

in the vicinity of the above 0 range and may suggest the existence of

3
[Ta(DPM)4][TaCl6] in the solid state. However, the low energy Shift of
12 cm.1 is also consistent with an increase in coordination number of

Ta from six to seven. Figure 8 shows the nmr spectrum of Ta(DPM)2C13 at
room temperature. One pfbutyl resonance at T 8.84 and one gamma proton
resonance at r 3.80 are present. The Efbutyl resonance occurs 33, 0.1
ppm upfield of the Efbutyl resonance for Ta(DPM)Cl4 (see Figure 5).

If equal amounts of neutral seven-coordinate species and the eight-
coordinate cation were present, as described in the equilibrium on p. 43,
at least two Efbutyl and gamma proton resonances would be predicted to
occur. Furthermore, the positive charge on the cation would effect a
downfield shift relative to the neutral Ta(DPM)Cl4 species. The
observed upfield Shift suggests that the equilibrium favors the seven-
coordinate species in dichloromethane. In view of the lower polarity of

dichloromethane compared to nitrobenzene, the solvent in which both

conductivity and molecular weight data were obtained, this result would

45

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49
be expected. Based on all possible sevenrcoordinate stereoisomers aris-
ing from a pentagonal bipyramid, capped octahedron, capped trigonal

prism, and tetragonal base-trigonal base, only the C trigonal prism,

2v
with a chlorine capping, a rectangular face and the three ligands spanning
equivalent rectangular edges, would account for the observation of one
Efbutyl line, in the absence of ligand exchange. The dichloromethane
solution was cooled to -60°C, but no new resonance or line-broadening

was observed. Consequently, there are two possible explanations for

the nmr Spectrum of the complex in dichloromethane, if one assumes that

the fortuitous existence of only the C isomer is unlikely. First, an

2v
intramolecular ligand exchange process may be invoked which would

average the pfbutyl environments of the seven-coordinate isomer.

This explanation would apply if an appreciable amount of eight-coordinate

cation was not present in solution. However, if one does assume the

presence of an appreciable amount of the cation, then an intermolecular

 

exchange process must be invoked to explain the presence of only one
Efbutyl line. In this case, the line would represent an average of the
‘EbetYI environments of both seven— and eight-coordinate Species. In
either case, the spectrum at -60°C indicates a rapid exchange process.

Appreciable decomposition of Ta(DPM)2C1 complex in dichloromethane

3
was Observed in the course of the nmr Studies. After 40 minutes of

aging, free ligand peaks at r 8.85 and 4.23 begin to appear, and after
4 months, they grow to an intensity equivalent to that of the original

‘EbetYI and gamma proton resonances. An identification of the Ta

decomposition product was not attempted.

50

2. The Reactions of NbCl: and H(DPM).

 

NbClS and neat H(DPM) react very vigorously with evolution
of HCl at room temperature. In order to control the reaction at a
convenient rate, the reagents were mixed in the presence of a solvent,
dichloromethane. At a molar ratio of NbCl5 to H(DPM) of 1:1.1, an
orange solution was obtained after a 30 minute reaction period. Addition
of hexane to the solution afforded a red-orange powder. The C, H, and
Nb analyses for the product were in acceptable agreement with Nb(DPM)C14
(see Table I), but as in the case of the analogous Ta derivative, the
chlorine analysis was anomalously low.

The infrared spectrum of Nb(DPM)C14 in solid state is shown in
Figure 9. The features of the Spectrum are qualitatively similar to the
Spectrum of the Ta derivative (see Figure 5). The diketonate ligand
is chelated, as evidenced by the positions of the C80 stretching modes.
The band due to overlapping frequencies for Nb-Cl and Nb-O vibrations
is positioned 22, 10 cm.1 higher in energy than the analogous band for
the Ta derivative.

Nb(DPM)ClA in the solid State rapidly hydrolyzes, upon exposure to
atmospheric moisture, to form HCl and a pale yellow residue. The
residue, however, contains coordinated DPM as indicated by infrared
spectroscopy. The intensity of the 360 cm.-1 band is markedly decreased
on hydrolysis, as expected for the loss of chlorine.

The nmr Spectrum of Nb(DPM)C14 in dichloromethane is Shown in
Figure 10. Two Efbutyl resonances are clearly resolved at T 8.72 and

8.69, and the presence of a third line is suggested by a shoulder on the

low-field side of the'r8.72 line. Two -CH- lines are present at r3.38

51

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55
and 3.47. The lines at T 8.72 and 3.47 are assigned to the complex;
the remaining lines are probably due to decomposition products. For
example, allowing the solution to age at room temperature for 24 hours
causes the line at 1 8.69 to increase in intensity. The decomposition
observed by nmr spectroscopy is consistent with the fact that Nb(DPM)C14
cannot be recrystallized from dichloromethane.

Shown in Figure 11 is the nmr spectrum of Nb(DPM)Cl4 after it had
been allowed to hydrolyze in the solid state by exposure at room
temperature to atmospheric moisture. The lines at T 8.84 and 3.80 are
identical in position to those observed for Ta(DPM)2Cl3, and the lines
at T 8.85 and 4.23 are those expected for free ligand. Thus it appears
that the hydrolysis of Nb(DPM)Cl4 leads in part to formation of H(DPM)
and the higher substitution product Nb(DPM)2C13, whereas the hydrolysis
of Ta(DPM)C14 forms an oxide or oxychloride not containing DPM.

The existence of a higher substitution complex of the type,
Nb(DPM)2C13, was also suggested by the appearance of lines at r 8.84
and 3.80 in the nmr spectrum of a Solution of Nb(DPM)C14 and free
H(DPM) in dichloromethane after it had been allowed to age 13 days at
room temperature. As noted above, these chemical shifts are identical
to those observed for Ta(DPM)2013.

The reaction of NbCl5 and H(DPM) at a molar ratio of l to 5
in dichloromethane at room temperature afforded an orange-
red crystalline product with a carbon and hydrogen content near that
expected for Nb(DPM)2013 (see Table I). The chlorine analysis is

characteristically low, and the Nb content is somewhat high. The presence

of an oxo impurity is indicated by a band at 807 cm"1 in the infrared

56

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58
spectrum of the product shown in Figure 12. A band in this region
(825 cm-1) for NbO(ACAC)2Br has been assigned by Djordjevic10 to a
Nb-O—Nb stretching mode. The oxo impurity probably is a decomposition
product of Nb(DPM)2C13, perhaps formed by abstraction of oxygen from
the diketonate ligand. Oxygen abstraction by Nb and Ta has been observed

previously with various solvents and donor ligands such as phosphine

42,43

oxides, sulphoxides,44 and beta-diketonates.11b The infrared

spectrum also contains a strong, broad band at 339 cm”1 which is
assignable to overlapping Nb-Cl and Nb—O stretching frequencies. AS
in the case of Ta(DPM)2Cl3, the possibility of the ionic formulation,

[Nb(DPM)4][NbC16], is suggested as the Nb-Cl stretch lies just outside

the range of 331-335 cm"1 for the v3 vibration of the NbCl6- ion.40’41

The reaction of NbCl5 and H(DPM) in dichloromethane at room tempera-

ture was also investigated at molar ratios of 1:3 and 1:10. The 1:3
reaction mixture, after a reaction time of 4 hours, afforded a mixture

of Nb(DPM)C14 and Nb(DPM)2C1 as indicated by elemental analyses and

3

nmr Spectroscopy. After a reaction of 26 hours, the 1:3 mixture afforded

primarily Nb(DPM)2C13:
6.77% H; nmr in CH2C12, T 8.84 and 3.80 with relative intensities of

18:1. The nmr spectrum of the 1:10 reaction mixture indicated the

Found; 46.60% C, 7.06% H; Calc'd, 46.70% C,

presence of only Nb(DPM)Cl4 after a 20 minute reaction time, approximately

equal amounts of Nb(DPM)C14 and Nb(DPM)2C1 after 3 hours, and only

3

Nb(DPM)2013 after 21 hours. The presence of excess free ligand in the

reaction mixture apparently retards the decomposition of Nb(DPM)2Cl3,
as well as Nb(DPM)C14. Figure 13 illustrates the rapid decomposition

of Nb(DPM)2C1 in dichloromethane in the absence of free ligand. After

3

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63
the solution has aged only 10 minutes an impurity line appears at T 8.71

and another appears as a low field shoulder on the r 8.84 line. After
three days both lines increase significantly in intensity and 3 —CH=
lines can be observed at T 4.23 and T 3.67 and r 3.80. The T 8.85 and
4.23 lines are characteristic of free H(DPM) and the T 8.84 and 3.80 lines
may be due to Nb(DPM)ZCl3.
The reaction of NbCI5 with H(DPM) was also conducted in the

presence of triethylamine at room temperature at a metal to ligand molar
ratio of 1:4.1 for 20 hours. In addition to the by-product triethylamine-
hydrochloride, a product, whose infrared and nmr spectrum was identical
to the Nb(DPM)2C13 complex above, was isolated. Thus, in spite of the
presence of base and a long reaction time, further substitution of
ligand for chlorine was not achieved.

3. The Reaction of Nb(DPM)4 and C12.

In an effort to prepare the chloride salt of the eight-

coordinate cation, Nb(DPM)4+, and verify the possible existence Of the
cation in the above syntheses, Nb(DPM)4 was oxidized by means of
anhydrous, oxygen-free chlorine. However, instead of the desired
salt, a compound with the stoichiometry, [NbOC12(DPM)]x, was prepared.
The progress of the preparation of this oxo-complex was monitored by
ear Spectroscopy. Immediately upon addition of the first aliquot of
chlorine solution, the deep purple (almost black) solution became blue-
green and remained this color when a sample was removed 40 minutes later.
The presence of Nb(IV) was still indicated by a 10 line esr spectrum,
and only after the solution became orange in color (3 hours later), was

the complete absence of the Signal observed. The golden yellow solid

that was isolated from the reaction mixture was sparingly soluble in

64
benzene (pg. 0.001 g/ml) and dichloromethane, and insoluble in either,
acetone, and carbon tetrachloride. The poor solubility properties of
the compound are, of course, consistent with a polymeric formulation.
The elemental analysis was also in agreement with the suggested formula—
tion. The infrared spectrum of the solid is shown in Figure 14. The
striking feature of the spectrum is the presence of a very strong,
broad band at 802 cm-1. This is assigned to a Nb-O-Nb stretching mode.
The two strong, broad bands at 350 cm"1 and 380 cm—1 are assigned to the
Nb-Cl stretching mode (the former band likely overlaps a Nb—O (ligand)
stretching mode). Both assignments are consistent with those made by
2 3.10 In the ACAC

complex, a strong, broad band at 820 cm-1, and a strong broad doublet at

Djordjevic for NbOCl ACAC which was prepared from NbOCl
355 cm.1 and 379 cm.1 were assigned to the Nb-O—Nb and Nb-Cl modes,
respectively. It is interesting to note that even the lower energy
band at 350 cm.1 for the DPM complex is still at a higher energy than
the band at 338 cm-1 assigned to the Nb-Cl stretching mode for Nb(DPM)2C13.
A weak nmr spectrum (due to low solubility) was obtained in dichloro—
methane. A multiplet of broad resonances was observed in the Efbutyl
region with at least 5 peaks resolvable at T 8.82, 8.77, 8.73, 8.72 and
8.70. This result is not unexpected since numerous isomers are possible
even when x is only 2. The nmr solution was too dilute to observe -CH=
resonances.

The preparation of this compound appears to be yet another example

of the tendency of niobium to abstract oxygen from a ligand (see p. 58).

65

g z

66

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67
4. Summary.
The preparation and characterization of a series of new
Nb(V) and Ta(V) complexes containing the beta-diketonate ligand, H(DPM),
have been described. Complexes of the type,.M(DPM)Cl4 and M(DPM)2C13,
were obtained by allowing the metal pentahalide to react with neat H(DPM)
(for M - Ta) and with H(DPM) in presence of dichloromethane as a solvent
(for M 8 Nb). The complexes of the M(DPM)ClA series exhibit similar
infrared and nmr Spectra, but the Nb derivative appears to be much less
stable in solution in the absence of free ligand. The above spectral
similarities and solution behavior also hold true for the M(DPM)2C1

3

series. Conductivity data indicate that Ta(DPM)2C1 is highly dissociated

3

in nitrobenzene and nitromethane solution: a dissociation equilibrium
involving Ta(DPM)4+ and TaCl6_ is suggested. The constitution of the
M(DPM)2C13 complexes in the solid state may correspond to an eight-
coordinate cationic salt, [M(DPM)4][MC16]. Evidence to support this
formulation is based primarily on the presence of a band in the ir
spectrum near that expected for TaCl6-. The inability to obtain a
higher substitution product in the presence of a large excess of ligand
(ligand to metal ratio of 10 to l) or in the presence of base also
suggests the ionic constitution of the complex. An attempt to prepare
the Nb(DPMM+ cation by reaction of Nb(DPM)4 and anhydrous, oxygen-free
C12 in CClA, led to abstraction of ligand oxygen by the metal and the

formulation of a polymeric oxo complex, [NbOC12(DPM)]x.

68

B. Preparation and Characterization of Tetrakis(dipivaloyl-

methanato)nlobium(IV)

The reaction of NbCl4 and H(DPM) was conducted in acetonitrile
in the presence of triethylamine. The procedure is analogous to that
used by Deutcher and Kepert118 in their preparation of other niobium(IV)
diketonates. Based on melting point, infrared, and ear data, the same
product was obtained upon varying the ligand to metal ratio from 10:1
(reaction time = 46 hours) to 4:1 (reaction time = 3 hours). In both
cases, the yield was between 50 and 60%.

An nmr spectrum of a dichloromethane solution of the dark purple
(almost black) solid Showed no free ligand resonances and elemental
analyses were obtained without prior recrystallization. The compound,
however, does form opaque, dark purple needles when recrystallized in
benzene-acetonitrile. In the solid state, Nb(DPM)4 apparently does
not undergo any decomposition when Stored under anhydrous, oxygen-free
conditions, as judged by comparison of the ir spectrum of a fresh sample
and one which had aged over 1 year. However, after several months of
exposure to air, the solid becomes coated with a white film, suggesting
that oxidation and/or hydrolysis occurs.

The compound is extemely soluble in most nonpolar organic solvents.
Deep purple solutions are formed which become yellow upon exposure to
air for several days. The infrared spectrum of a yellow dichloromethane
solution shows a Strong broad band at 800 cm"1 as well as bands at 1700
and 1730 cm-1. The same Spectrum is obtained when oxygen is bubbled into
a dichloromethane solution of Nb(DPM)4. The band at 800 cm"1 suggests

an oxidation to some type of bridging oxoniobium(V) species (see

69
SE=<:tion II). The bands at 1700 and 1730 cm"1 suggest..a Nb by-product

tlnuat has a free carbonyl function or, perhaps, the by-product is free

I"I‘IDPM.

Deutscher and Kepert11b report that Nb(ACAC)4 also decomposes in
‘Vaet solvents. NO mention iS made of the behavior in anhydrous solvents,
laut one must infer that the complex is stable, since solution spectral
(flats in toluene are reported. It is interesting to note that the
.authors report that Nb(ACAC)4 in the solid state decomposes rapidly in
air, in contrast to Nb(DPM)4. Thus with the successful synthesis of
such an unusually stable Nb(IV) beta-diketonate, a stereochemical
investigation was eagerly undertaken.
The infrared spectrum of Nb(DPIM)4 is shown in Figure 15. Since no
absorptions are observed in the carbonyl region (1600-1720 cm-l) of the
free ligand, chelation by the beta-diketonate ligand is indicated. The

1

carbonyl stretching modes are assigned at 1585 cm" , 1562 cm-1, and

1410 cm.1 which is consistent with previously reported assignments for

transition metal beta-diketonates.35’36

The low energy portion of the
Spectrum shows two absorptions at 352 cm-1, and 285 cm”1 which are
aissigned to Nb-O (ligand) Stretching modes. These assignments are
(:onsistent with the analysis of the low energy portion of the infrared
sspectra for the niobium(V) complexes described in section IV-A.2.

The molecular weight was determined in benzene because the hydrolysis
10f Nb(DPM)4 appeared to occur less rapidly in this solvent than in other
solvents. The observed value of 777 g/mole is in agreement with the
“value expected for a monomer (826). The molar conductance

1 3

(0.0901 ohm-1cm2mole- , 2.93 x 10- M) is consistent with a non-electrO*

1yte in dichloromethane. Fay and Lowryl‘5 report A to be 0.092

7O

.Hasa Hemsz m as «AZmonz mo enuuooom commuon

.mH mesmem

71

5.0

coop

 

 

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72

3

(5 x 10—3 M) for the non-electrolyte, Ti(ACAC)C12, and 40 (5 x 10- M)

for the 1:1 electrolyte, ISiCACAC)3JBr, in the same solvent. A time
dependence is observed for the conductivity of Nb(DPM)4 in dichloro-
methane. The initial value ofll reported above was observed 7 minutes
after the preparation of the solution. After aging for 15 minutes, A
increased to 0.169 ohmfllcmzmole-l, after 50 minutes to 0.326, and after
9 days the deep purple solution had changed to a yellow-brown color,and
A had increased to 13.3. After 10 days of aging, the color became
yellow, and A bad leveled off, as indicated by a value of 13.2. Thus,
the time dependence was due to oxidation,and poSsibly hydrolysis,upon
aging in the conductivity cell (see ir data above). The value of 6.88
(1.11 x 10-4 M) reported for Nb(DPM)4 in nitrobenzene was Observed
after the solution had aged for 60 minutes and hydrolysis had likely
already occurred to a Significant extent.

The room temperature effective magnetic moment of Nb(DPM)4 was
determined by both the Evans and Faraday technique. In view of the
comparable magnitudes of the paramagnetic and diamagnetic molar
susceptibilities (see Section III), the observed values of 2.1 B.M.
(Evans) and 1.9 B.M. (Faraday) are consistent with one unpaired electron.

Consequently, all of the above preliminary experiments (infrared,
molecular weight, conductance, and magnetic susceptibility) are
consistent with a discrete molecular eight-coordinate formulation for
Nb(DPM)4 and a +4 oxidation state for the Nb atom.

C. The.X-Ray Structure Determination of Nb(DPM)4

Nb(DPM)4 crystallizes in the space group, Pc, with four

molecules in the unit cell and two molecules in the asymmetric unit.

73

The experimental density is 1.123 cm.-3 (p = 1.12g cm-3) and the

calc.

unit cell dimensions are as follows:

a - 22.30 i 0.05 I
b - 11.86 i 0.02 A
c - 19.58 i 0.05 3.
B - 107.46 : o.05°

Table IIA and B lists the final atomic coordinates, thermal
parameters, and electron density of the 106 atoms comprising the two
molecules in the asymmetric unit. The Observed and calculated structure
factors are listed in Appendix B. Tables III-VII list the bond distances
and angles of both molecules. The interior angles of planes of the
Nb(DPM)4 polyhedron are listed in Appendix C. Figures 16a and b and 17a
and b illustrate the electron density contour maps of the two molecules
obtained from the observed Fourier map with an R factor of 0.086.

The motions associated with the transformation of a cube into a
D4d square antiprism or a D2d dodecahedron are shown in Figure 18. The
structure of Nb(DPM)4 appears to approximate the square antiprismatic
geometry. A convenient perspective for viewing the square antiprism
is along the fourfold rotation axis (C4). This view of the two molecules
comprising the asymmetric unit of the unit cell (molecules A and B) is
shown in Figure 19. It is clear from this representation that the
structure may be visualized as a "propeller" or "pinwheel" with idealized
D4 symmetry. However, because the dodecahedron is so closely related

to a square antiprisml—Ba’4

(a square antiprism with puckered square
planes may be viewed as a dodecahedron), it is necessary to consider

the Nb(DPM)4 Structure in terms of the most closely related dodecahedral

isomer(s) to unambiguously establish it as an idealized D4 square

74

 

 

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79

Table II(B)

the Chelate Rings in Nb(DPM)4

Electron Densities (p) for Atoms Comprising

 

Atom Molecule A Molecule B
Number
Nb 44.53 41.9
01 6.1 5.5
02 7.0 6.5
03 5.7 6.2
04 5.3 6.1
05 6.4 6.3
06 6.2 6.4
07 5.9 6.4
08 6.1 6.4
Cl-l 4.1 4.1
02-1 3.9 3.8
C3-1 3.5 4.0
01-2 4.5 4.3
C2-2 4.1 4.0
C3-2 3.6 3.9
01-3 3.6 3.6
02-3 3.5 3.9
C3-3 4.0 4.8
C1-4 3.1 3.7
02-4 4.0 4.6
03-4 4.2 4.5

2-Corrected for F

80

Table III

Nb-O and 0-0 Distances A in Nb(DPM)4

 

 

 

Molecule A ' Molecule B
Atom Distance Atom Distance
Number (A) Number (A)
Nb-O Distances

Nb-01 2.1843- Nb-01 2.132
Nb-OS 2.104 Nb-05 2.062
Nb-06 2.138 Nb-06 2.131
Nb-03 2.091 Nb-03 2.136
Nb-07 2.192 Nb-07 2.068
Nb-04 2.044 Nb-O4 2.172
Nb-08 2.131 Nb-08 2.160

b

Mean Distance: 2.128 i_0.04£#E 2.128 t 0.042—

0-0 Distances Along Diagonals of Square Face

01-03 3.438E 01-03 3.547
02-04 3.447 02-04 3.580
05-07 3.612 05-07 3.471
06-08 3.719 06-08 3.623

b

Mean Distance: 3.554 1 0.136— 3.555 _+_ 0.064-11

0-0 Distances Defining Chelate Bites

01-05 2.7692. 01-05 2.687
02-06 2.718 02-06 2.778
03-07 2.789 03-07 2.707
04-08 2.634 04-08 2.789
b b

Mean Distance: 2.728 :_0.069- 2.740 i_0.051—

0-0 Distance DefiningLateral Edges Not Involving Chelate Bites

01-08 2.712 01-08 2.652
02-05 2.672 02-05 2.651
03-06 2.642 03-06 2.692
04-07 2.674 04-07 2.687

Mean Distance: 2.675 i_0.029§

2.670 3: 0.0223-

b

I03

IO‘

In

81

Table III (cont'd)

 

Molecule A Molecule B
Atom Distance Atom Distance
Number (A) Number (A)

0-0 Distances Defining Edges of Sguare Faces

01-02 2.437 01-02 2.506
02-03 2.491 02-03 2.530
03-04 2.324 03-04 2.519
04-01 2.491 04-01 2.525
05-06 2.643 05-06 2.490
06-07 2.574 06-07 2.487
07-08 2.621 07-08 2.553
08-05 2.540 08-05 2.506

Mean Distance: 2.515 i 0.1042 2.514 i 0.0222

The average standard deviation for a single Nb-O distance
as calculated from the uncertainties in atomic coordinates
(equations on p. 417 of ref. 33), 13 :_0.020 A.

/2

Standard deviation (0) of the mean (0 = [Xoi/n-l]1 ).

Based on uncertainties in atomic coordinates, the average
standard deviation of a single 0-0 distance is
i 0.030 K.

82
Table IV

DPM Ligand Bond Distances (A) in Nb(DPM)4

 

 

 

 

Molecule A a Molecule B
Atom Ligand Number—- Atom Ligand Number
Numbers 1 - 2 3 4 Numbers 1 2 3 4
C-0 Distances
01-0 1.2532 1.237 1.397 1.494 c1-0 1.261 1.390 1.388 1.216
C3-O 1.358 1.316 1.130 1.202 C3-0 1.202 1.308 1.333 1.217
Mean Distance: 1.298 1 0.1172 1.290 i 0.0772
C-C Distances in Chelate Ring
C1-C2 1.528§.1.353 1.367 1.408 Cl-CZ 1.357 1.339 1.500 1.395
C2-C3 1.447 1.317 1.346 1.411 C2-C3 1.508 1.445 1.377 1.374
Mean Distance: 1.397 1 0.0612 1.412 :_0.0652
C-C Distances in Terminal t-Butzl Groups
Cl-C8 1.5852 1.558 1.532 1.514 C1-C8 1.630 1.537 1.574 1.473
C8-C9 1.643 1.604 1.714 1.348 C8-C9 1.528 1.498 1.525 1.410
C8-C10 1.289 1.651 1.522 1.715 C8-C10 1.499 1.659 1.693 1.764
08-C11 1.504 1.441 1.559 1.555 C8-Cll 1.612 1.663 1.698 1.578
C3-C4 1.473 1.574 1.656 1.595 C3-C4 2.045 1.537 1.683 1.476
C4-CS 1.833 1.496 1.434 1.564 C4-C5 1.432 1.512 1.549 1.486
C4-C6 1.421 1.666 1.640 1.507 C4-C6 1.994 1.611 1.383 1.491
C4-C7 1.476 1.689 1.696 1.435 C4-C7 1.116 1.636 1.889 1.576
Mean Distance: 1.559 t 0.0943 1.586 i 0.1801

IO‘IN

IQ-ln

ring is + 0.060 A.

lm

Ligands are defined in Figure 19.

Standard deviation of the mean, 0 a 2(012/n-1)

terminal t-butyl groups is i 0.150 A.

1/2

Based on uncertainties in atomic coordinates, the average
standard deviation33 of a single C-0 distance is + 0.040 A.

Average standard deviation of a single C-C distance for the

Average standard deviation of a single C-C distance in a chelate

83
Table V
0-Nb-0 Angles in Nb(DPM)4

Angle, degrees Angle, degrees
Atom Numbers Molecule A Atom Numbers Molecule B

 

 

 

O-Nb-O Angles of Chelate Rings

Ol-Nb-OS 80.4 Ol-Nb-OS 79.7
02-Nb-06 79.1 02-Nb-06 80.7
03-Nb-07 81.2 03-Nb-07 80.1
04-Nb-08 78.2 O4-Nb-08 80.1
Mean Angle: 79.7 : 1.$E Mean Angle: 80.2 :_0.4

O-Nb-O Angles between Chelate Rings

03-Nb-06 77.3 03-Nb-06 78.2
04-Nb-07 78.2 04-Nb-07 78.6
01-Nb-08 77.9 01-Nb-08 76.3
Mean Angle: 77.9 i 0.4 Mean Angle: 77.7 i 1.0
Mean of all Angles: 78.8 i;1.3 ‘Mean of all Angles: 78.9 1:1.5

é-Standard deviation of mean

84

Table VI
Chelate Ring Interior Angles in Nb(DPM)4

Angle, degrees
Molecule A

 

Atom
Numbers

L1 L2
Nb-O-Cl 131.9 129.
Nb-O-C3 140.4 131.

Mean Nb-O-C Angle:

L1 L2

0-C1-C2
0-C3-C2

Mean O-C-Cr Angle:

L1 L2

Cl-CZ-C3 123.7 120.7 122.5 128.5 Cl-C2-C3 122.2 121.3 117.3 126.5

Mean C-Cr-C Angle:

 

Nb-O-C Angles

L3 L4

5 128.8 136.2
3 130.6 141.1

133.7 2“. 4.9

O-C-Cr

L3 L4

125.6 130.9 124.3 115.0
118.1 125.1 131.8 119.7

123.8 2‘. 5.9

C-Cr-C Angles

L3 L4

123.8 1 3.3

Atom Angle, degrees
Numbers Molecule B

L1 L2 L3 L4
Nb-O-Cl 132.8 130.3 134.3 132.5
Nb-O-C3 139.6 132.0 133.7 133.2
Mean Nb—O-C Angle: 133.6 112.6
Angles

L1 L2 L3 L4
0-Cl-C2 124.9 127.9 123.4 121.3
0-C3-C2 120.2 127.1 129.7 123.0
Mean O-C-Cr Angle: 124.7 i_3.3

L1 L2 L3 L4

Mean C-Cr-C Angle: 121.8 1 3.8

85

Table VII

Average Bond Distances and Angles in the Nb-DPM Chelate Ring

° Average over

 

 

 

 

Distance, A Molecule A. Molecule B both Molecules
Nb-O 2.128 1 0.048 2.128 i 0.042 2.128 j; 0.045
0-0 2.728 :_0.069 2.740 :_0.051 2.734 :_0.060
(ligand bite)
C-O 1.298 :_0.117 1.290 :_0.077 1.294 1 0.096
C_Cr9. 1.397 2‘. 0.067 1.412 _+_ 0.065 1.404 1 0.064
C-Ct 1.553 1 0.056 1.619 : 0.186 1.586 _+_- 0.136
Ct-Cm 1.558 3; 0.131 1.575 :1; 0.173 1.566 _-_1-_ 0.151
Angle, deg. Molecule A Molecule B 88:88:81:::1es
0M0 78.8 i 1.3 78.9 i 1.5 78.8 i 1.4
(79.7 i 1.3)E (80.2 i 0.4) (80.0 _+_: 0.9)
MOC 133.7 1 4.9 133.6 1 2.7 133.6 3; 3.8
OCCr 123.8 f; 5.9 124.7 1 3.3 124.2 _+_: 4.7
CCrC 123.8 1 3.3 121.8 -_+_ 3.8 122.8 3; 3.5
2.

C, Cr’ Ct’ and Cm denote carbonyl carbon, ring carbon, tertiary-

butyl carbon, and methyl carbon atoms, respectively.

2 ( ) denotes the chelate ring angles only.

Figure 16a.

86

The composite electron density along the

b axis for Nb(DPM)4, Molecule A, showing
the half of the molecule containing ligands
L1 and L2. With the exception of Nb,
contours are at 1 electron/(A)3 beginning
with 1 electron. For Nb, contours are at

4 electrons/(A)3 beginning with 1 electron.
The ligand number corresponds to the last
number of each carbon atom.

 

 

 

87

 

 

16a

Figure

 

 

88

Figure 16b. The composite electron density along the
b axis showing the half of Molecule A
containing ligands L3 and L4; contours as
in Figure 16a.

 

 

 

 

 

 

90

Figure 173. The composite electron density along the
b axis for Nb(DPM)4, Molecule B, showing
the half of the molecule containing
ligands L1 and L2; contours as in 163.

92

Figure 17b. The composite electron density along the b
axis showing the half of Molecule B containing
ligands L3 and L4; contours as in Figure 16a.

94

H.8mfiuofiucm mumsom can mam coummsmowmov mun
m cu onso m mo coaumahowmamuu mnu nufi3 woumfioommm maOfiuoa 0&8

.mH maawem

95

 

 

 

 

 

 

 

 

 

 

 

Figure 18

 

96

Figure 19. A view of the "idealized" D4 square antiprismatic
coordination polyhedron down the"pseudd'C axis
including the numbering scheme for the ligands,
oxygen atoms and carbon atoms for Nb(DPM)4. The
b axis is indicated.

 

97

 

 

 

 

L4

 

()4 ()3

@ L3

 

Figure 19

 

98

antiprism. To do this, we must consider the merit of the two most
closely related dodecahedral stereoisomers:2’3a the D2(gggg), and the
D2 (aabb) dodecahedron. These isomers, along with the remaining
stereoisomers possible for a tetrakis chelate, are illustrated in
Figure 1. The polyhedral shape parameters that must be calculated to
distinguish between the three possibilities are the angles defined by
the metal ligand bond axis and the principal rotation axis of the
idealized polyhedron, the degree of planarity in the trapezoidal planes
of the dodecahedra and the square planes of the antiprism, and the
angles of intersection of these planes.

Hoard and Silverton3a have defined the dodecahedron in terms of two
angles, 6A and GB,
bonds, M-A and M-B, with the fourfold inversion axis (4) and the ratio

formed by the two unique types of metal-ligand atom

of the M-A and M-B bond lengths (see Figure 20).

In addition, the four unequal edge lengths of the dodecahedron, a,
b, m, and g are useful in discussing the polyhedron deSpite being
redundant in terms of defining it. The definitive shape parameters for
the square antiprism are the angle, 6, made by a metal-ligand atom
bond, M-A, with the 8 axis (for a D4d square antiprism) and the ratio
of the lateral edges, 1, to the square edges, 8 (see Figure 20). Once
the above parameters have been determined, a choice of the prOper poly-
hedron may be made on the basis of a comparison to those calculated for
models based on a closed-shell, non-bonded ligand repulsion analysis
that minimizes ligand repulsions. These parameters are referred to as the
"most favorable" polyhedron parameters by Hoard and Silverton.3a

Recently, Lippard and Russ“6 have suggested a third criterion for

99

.Emauofiuam mumsum woo com couwmsmowwom mma oxo

pom Coaumuoc Homoemuma momcm Hmummfimaoo mmcouum>flwm mam wumom 0:9

.oN magmas

100

 

om muswwm

u

N

 

 

 

 

 

101
distinguishing dodecahedral and square antiprismatic stereochemistry
in cases where the criteria of Hoard and Silverton may not provide an
unambiguous choice. Lippard and Russ point out that one of the draw-
backs of the Hoard and Silverton criteria is that the 8 axis of the

D4d square antiprism and the 4 axis of the D d dodecahedron are mutually

2
orthogonal and thus, direct comparisons of the 6 angles are not mean-
ingful. Furthermore, although calculations of edge lengths are
normalized by the metal-ligand atom bond distance, ambiguities arise
since the dodecahedron does not possess a single value for this distance
as does the antiprism. Further problems arise due to the presence of
four non-equivalent edges (a, b, m, g) in the dodecahedron and only two
(1, s) in the antiprism. Consequently, to complement the polyhedral
selection, the authors suggest trapezoidal planes, whose line of
intersection contains the central metal atom (as described by Board and
SilvertonBa) and coincides with the 4 axis. Once the best planes
corresponding to the two trapezoids have been calculated, the angle of
intersection of these planes may also be calculated and compared to the
theoretical values of 90° and 77.4° for the perfect dodecahedron and
square antiprism, respectively. This procedure, however, also has its
disadvantages since the angle of intersection of the trapezoidal planes
is only theoretical, i.e., it is a result of two nonexistant planes
when the polyhedron is actually a square antiprism. It would seem that
the most definitive test would be to calculate both the trapezoidal
planes of the polyhedron viewed as a dodecahedron and the square planes
of the polyhedron viewed as a square antiprism, and then to compare the
deviations from these beat planes. In addition, the deviation of the

angle of intersection of the square planes from 0° would provide a good

102
criterion for the prOper choice.

Tables VIII-X list the edge lengths used to calculate shape para-
meters for the three polyhedra being considered. It is obvious that
for each polydron, both molecules (A and B) must be considered, and in
the case of the dodecahedral stereoisomers, there are two sets of
trapezoidal planes (Sets I and II) which can be defined. Tables XI
and XII list the deviations of the oxygen atoms comprising the possible
dodecahedral planes from the best plane and also the angles of inter-
section of these planes. Table XIII lists the deviations of the oxygen
atoms comprising the two square planes of the square antiprism, the
angles of intersection of these planes, and the shape parameter, 8, as
defined above. Tables XIV and XV summarize the results of these data
and compare them to the idealized polyhedron shape parameters.3a’46
The average Nb-O bond lengths which were identical (2.128 A) in molecules
A and B were used to normalize the shape parameters.

An analysis of the results of the above calculations clearly
establishes the structure of Nb(DPM)4 to be most closely approximated
by the D4 square antiprism. The overall agreement between the experi-
mental and "MP?" shape parameters for a square antiprism is good.

However, the most striking evidence to support the choice of the square
antiprism lies in the plane calculations. The maximum average deviation
from planarity for four oxygen atoms comprising a square plane is 0.058 A,
whereas the minimum average deviation from planarity for four oxygen
defining a trapezoidal plane is 0.26 A. Furthermore, the square planes
are parallel in molecule A(a8 - 0°) and very nearly parallel in molecule
B (018 = 0.7°). Among the various dodecahedral views of the molecule,

the best trapezoidal planes, which should be orthogonal, intersect at a

103

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.mH ouswwm ou wofivuooom :OHuMuoz

UI

 

 

 

3
.mm monoummou ou wcfivuooom cofiumuoz.m

Aoeo. + mmm.NV Aema. + Nem.~v flame. + mem.~v Ammo. + mac.mv w
eme.~ eem.~ mus mmn.~ Hee.~ ens mm
eon.~ oen.~ mum omm.~ Hee.~ mum em
eem.~ amm.~ hue mmm.~ HNc.~ eta mm

bom.N eme.~ ~-H oee.m mec.~ cum aw
~me.~ NHA.N ens Nme.~ NHA.~ and mm
ewc.~ eee.~ Ana emc.~ aeb.~ nus Ne
Nec.~ Nec.~ cum Nae.~ Nee.~ bum Hm
Hmb.~ Nec.~ m-~ |.Hme.~ ch.~ m-~ m

fibeo. amm.~v Ammo. ~em.~V Ammo. + eom.Nv AmHH. ace.mv e
mmm.~ HNe.N mun ewe.~ eem.~ “no me
cmm.~ Hee.N mum eon.m eme.~ ~-H Na
mum.~ Hee.~ cue eam.~ emm.~ mus Ha
oee.~ mec.~ bum 1.80m.~ oem.~ sum 8

Amee. Nea.mv abmm. oma.mv Amen. + moH.mV Anna. NmH.mv a
m~c.m eea.m m-e aam.m wme.m mus ma
owm.m nae.m elm Hee.n Nac.m sum up
ewe.~ eme.~ mus hom.~ ema.~ hum Ha
mee.~ mae.~ bum ..ewe.~ ..ebe.~ mus a

Aeao. nec.~v Aeao. eee.~v Acme. + eme.~v .wheno.+ cec.~v N
hoe.~ eme.~ e-m eme.~ emb.~ eta Ha
Awe.~ eee.~ m-H whe.~ mam.~ cum 6

m oasomaoz < masomaoz mumnEdz m masomaoz 4 masuoao: Mmuonaaz

HH umm Hmwfioummmua acu< cmwmxo H umm Hmmfioummdua aou< sow%xo mmwmm

aoumonmomwon Annmmvmn m mm woBmH> ma «Asmnvpz :05: A<V mnuwcoq omwm Hmummshaom
O

HHH> maamH

104

.HHH> mHQmH mom |

 

 

 

o .m.am

Rama. + eNc.NV AeNH. + emc.~v Acme. + emc.~v Aace. + eac.uv m
Hme.~ omn.~ mum mam.~ emm.~ eum em

Hee.~ mmm.~ ens com.~ eme.N mus cw

eem.~ eme.~ hub mmm.~ Hme.~ wue mm

oem.~ eom.~ mum oee.~ mec.~ cum em
eme.~ ame.~ m-e awe.~ emc.~ mue mm

eme.~ ace.~ hum Ace.m emm.~ hum N»

mee.~ mee.~ mum wee.m wae.~ c-~ Hm

ee~.~ emc.~ mne n.eme.~ |.eem.~ mus w

Anna. eom.Nv Aemo. ham.mv Aeao. NHm.NV Aaeo. + amm.~v e
emm.~ eam.~ aum eme.~ eem.~ sue me
mec.~ oee.~ btm mum.~ Hme.~ eta Na
Hmc.~ mmm.~ mne omm.~ Hae.~ mum Ha
eme.~ com.~ N-H a.com.~ u.oem.N mum a

Aehm. eeo.mv Amom. eeo.mv Ammm. w~a.mv Aemm. + wNH.mV e
eme.u Nea.m sum m~e.m eas.m muc ma
owm.m ~H6.m e-m nem.m mme.m mus Na
Hee.m emc.~ hue Nee.u Nee.m cum Ha
eec.~ Hmc.~ m-~ .n ~me.~ .I NHA.~ m-H a

Aeeo. eac.~v Ammo. Nec.~v AmNo. ebc.~3.mfiaoo. + mec.mv N
Nec.~ Nee.N bum mmc.~ ehc.~ hue Ha
~HA.~ Nnc.~ w-H Hnb.N Nec.~ mum n

m manomaoz < masomaoz muonssz m manumaoz < maaooaoz mononesz

HH uom Hmwfionmmmua acu< comaxo H umm Hmvfioummmua Eou< Gowhxo mommm

NH mHan

cosmosmommon Awwmwvmn m mm mo30a> ma «Aimnvnz 60:3 A¢V unawaoq mmmm Hmumozaaom
O

105
Table X

0
Polyhedral Edge Lengths (A) when Nb(DPM)4 is Viewed

as a D4(1111) Square Antiprism

 

Edge2 Oxygen Atom Molecule A Molecule B
Numbers—

11 1-5 2.769 2.687

12 2-6 2.718 2.778

13 4-8 2.634 2.789

14 3-7 2.789 2.707

15 1-8 2.712 2.652

16 2-5 2.672 2.651

17 3-6 2.642 2.692

18 4-7 2.674 2.687

(2.728 i .069)2 (2.740 1 .051)

31 1-2 2.437 2.506

52 2-3 2.491 2.530

33 3-4 2.324 2.519

34 1-4 2.490 2.525

35 5-6 2.643 2.490

86 6-7 2.574 2.487

37 7-8 2.621 2.553

38 5-8 2.540 2.506

(2.514 :1; .104) (2.514 : .021)

2’ 2’ E-See Table VIII

106

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.H .o: woman HmvwonomuH

UI

 

 

 

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8N.mm ow.mm oe.mm mo.mN wannabe .Ha

mNNNo.o NNmNo.o omHNo.o maemo.o an can

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seem.ou oNNe.o- m eNem.o eNmm.o a
Nmem.o ONee.o N eacm.o: econ.ou N
NNNN.o- meom.o- e NNeN.o eHaN.o m

2N8. H 83.8 888. H 88.8 380. H 83.8 Macao. H 82.8 .618
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NNaN.ou mNNN.o N NmmN.o NNON.o H

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coauommumucH mo moawc< mom mocmam HmmwoumomuH umom Boom mEou< amwkxo mo A<v maofiumfi>on
O

Hx manmh

107

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U

.m.vcm.m mmuoouoom .HHH> 0Hnma 00m I..I

 

 

 

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coauu0mu0uoH mo m0ch< mam 00:0Hm Hmmwon0omue um0m Eoum maou< a0wmxo mo A<v maowuma>0o
0

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a .n

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ONNN.N- NNNN.o- NNNNo.o NNeNo.o He men

5.8. H 0388 A88. H NNNN.8 88. H N388 GNNN. H 88.8 8
NNNN.o- NNNN.o- a NNNN.N- NNNN.o: N
NNNe.o NNNe.o N oeNe.o NNNe.o N
NNNe.on N4NN.N- N Nose.ou Neoe.on N
NNNN.o NNNN.o N eNNN.o NNNN.o N

ENo. H 32.8 GNNN. H NNNN.8 fiNNNo. H 83.8 mSNNo. H $2.8 m3
eNNN.ou NNeN.ou N NeNN.o NNNN.o N
NNoa.o Noem.o N NNNe.ou NNNa.ou N
NNNe.o: NNNe.ou N eNHe.o eNNe.o e
NNNN.o NNNN.o N eNNN.ou NNNN.on N

m 0H500Hoz < 0H300Hoz u0nadz m 0H500Hoz. < 0H900Hoz mu0nasz

HH u0m Hmwfion0m0ue aou< :0whxo H u0m Hmmfiou0m0uw Ecu¢ c0w%xo

108
Table XIII

Deviations (A) of Oxygen Atoms From Best Square Planes,
Angles of Intersection (as) of the Planes,
and the Shape Parameter Angles (6) when Nb(DPM)4 is Viewed as

a D4(1111) Square Antiprism

 

 

Oxygen Agom Molecule A Molecule B
Number-
1 0.04566 -0.01690
2 -0.04565 0.01686
3 0.04789 -0.01678
4 -0.04790 b 0.01681
(1)2. (0.04678 i;.00130)— (0.01684 i;.00005)
5 -0.0S807 0.01501
6 0.05730 -0.01511
7 -0.05777 0.01474
8 0.05854 -0.0l464
(2) (0.05792 3: .00052) (0.01488 1 .00068)
cos as 1.0000 0.9999
08, degrees 0 0.6836
Oxygen 6,2-Molecule A 6, Molecule B
1 52.73 56.66
2 54.63 55.83
3 54.33 55.76
4 56.70 55.60
5 58.80 57.18
6 60.69 57.16
7 55.62 57.18
8 60.50 58.07
(56.75 :_2.97) (56.68 1:0.77)
8!

IG-IO

Square plane (1).

See Table VIII, Footnotes b_and 2,

Defined according to reference 33; the C4 axis was the
best least squares line passing through the centroids
of the two square planes and the Nb atom.

109

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Amwmwvwo 0Hnwmwoo vcou0m 0nu pom .«onmo mam .monuo .maoum a0whxo ha v0afim0v m0aHH 0su mo muawoovaa

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«.mn m.mm N.oh «.mo m
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m.mm m.wm 0.08 m.oq <
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mH.H mH.H mH.H o~.H
BH.H wH.H mH.H wH.H 0H.H a mH.H wH.H wH.H m
oq.H oc.a om.a sq.H
m¢.H n¢.H sq.H oq.a we.a p
o~.H 0N.H mN.H Hm.H
NH.H m~.H o~.H Hm.H M¢~.H 0 o~.H m~.H wN.H H
mmz m 0H300Hoz. 4 0H=o0aoz m 0H300Hoz 4 oasomfioz mm: m 0H300Hoz, < 0H900Hoz
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>Hx 0H30H

110
Table XV

Experimental and Idealized Plane Deviations (A) and Angles of

Intersection for Nb(DPM)4 Viewed as a D Square Antiprism

4
and a D2(aabb) and D2(gggg) Dodecahedron

 

Molecule A Molecule B Idealized
fi‘fi‘ . in. j ' _ fl _ 1, e}_, . ‘ - Polyhedron
D4(llll) ds(1) 9- 0.058 0.015 0
63(2) 0.047 0.017 0
as 0.00° 0.68° 0
D2(aabb) dT(1) 9- 0.26 0.32 0(0.4)-E
. 0.37 0.32
dT(2) 0.26 0.31 0(0.4)
0.36 0.30
6T 85.0° 86.0° 90.0(77.4)9
85.8° 85.2°
D2(gggg) dT(1) 0.35 0.34 0(0.4)g
0.33 0.33
dT(2) 0.34 0.35 0(0.4)
0.33 0.34 ‘
6T 85.2° 85.0° 90.0(77.4)Si
85.5° 85.9°

-2 Average deviation of the 4 oxygen atoms (A) comprising the square plane
as defined in Table XIII.

2-Average deviation of the oxygen atoms comprising the trapezoidal plane
defined in Tables XI and XII: the two rows per plane correspond to the
two possible dodecahedral sets which can be derived from a D4 antipris-
matic configuration.

£-( ) represents deviation from planarity of the theoretical trapezoidal
plane derived from a perfect antiprism.

é-(_) represents the angle of intersection of the two theoretical trape—
zoidal planes derived from a perfect square antiprism.

111
maximum angle of 86.0°. The chviation of this angle from the perfect
antiprism value of 77.4° exemplifies the caution which should be

exercised when one chooses to use QT as a criterion to aid a polyhedral

selection. As discussed above, a is an angle based on theoretical

T

planes when the isomer is a square antiprism and consequently, would

 

be expected to deviate significantly from ideality as minor distortions
are introduced into the square antiprismatic polyhedron. The structure
of the bis (4-picoline) adduct of tris (2,2,6,6-tetramethyl—3,5-heptane-
dionato)ho1mium(III)47 is another example where the utility of this
angle is found to be secondary to the planarity criteria in aiding a
stereochemical assignment. The structure was determined to be a square
antiprism with the theoretical trapezoidal planes intersecting at an
angle of 85.8°. The average deviation from planarity for the square
planes was only 0.06 A, however, whereas the deviations of the best
trapezoidal planes ranged from 0.29 to 0.47 A.

It is strikingly obvious from the electron density contour maps
(see Figures 16 and 17 and Table IIb, that as one leaves the inner
coordination sphere of the Nb(DPM)4 molecule, the electron density
falls off significantly for the carbon atoms. For example, Figure 17a
shows a density for a t-butyl carbon, C3-l, of three electrons per cubic
Angstrom. However, the density of one of the methyl carbon atoms,
C6-1, belonging to the same ligand has fallen to one electron. With
the exception of the Nb atoms, in fact, the electron densities of all
the atoms are lower than expected. This phenomenon may be attributed
to a significant degree of disorder introduced into the molecule by
the abundance of tfbutyl groups. No previous structure with four DPM

ligands per molecule has been reported, but seven-coordinate monomeric

112
and dimeric lanthanide metal-DPM structures have been reported with
unusually high thermal parameters for the t-butyl carbon atoms.48_50
Erasmus and Boyens48 suggest that for the Dy(DPM)3H20 structure, the
high thermal parameters may be symptomatic of static disorder rather
than thermal vibrations. To support this hypothesis, the authors cite
the noticeably lower thermal parameters for several methyl carbon atoms
of the t-butyl groups. Bennet, E£_élr?1 also report a similar effect
for the CF3 groups in Cs[Y(HFA)4]. Although the thermal parameters of
the methyl carbon atoms of the t-butyl groups in the Nb(DPM)4 structure
were also high, no unusually low values were observed. Thus, it is
not clear whether the disorder is static or due to thermal vibrations.
The effect of the disorder is evidenced by the large standard deviation
for the carbon-carbon single bond distance which is shown, along with
the other average bond distances and angles, in Table III-VII and
Figures 21 and 22. Despite the large standard deviation of the mean
Q: 0.15 X) for the methyl carbon single bond distance, the average bond
distances and angles are in satisfactory agreement with previously

reported DPM-chelate structures.47-So’52’53

Furthermore, since the
question of which polyhedron best describes the structure is dependent
primarily on the accuracy with which the inner coordination sphere has
been determined (i.e., the oxygen positions), the inability to precisely
determine the carbon atom positions was only a minor disappointment.

As Tables III and IV indicate, the Nb-O bond length has been
determined to a much greater degree of precision than the C-C single

bond length. Since this is the first crystal structure of a Nb beta-

diketonate, a direct comparison of Nb-O bond lengths is not possible.

113

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000cmumav moon moan 0umH0£o Am mam < 00H900Hoa u0>ov 0mmu0>0 0:9

.HN anaNNm

114

NN magmas

 

115

.qAZmovaz CH moan mumfimsu
0cm «0 m0awam uoau0uca Am cam < m0H=o0Hoz u0>0v 0wmu0>m 0:9

.NN answam

116

mm one»:

   
 

odHodm

 

 

Ewe-N. 6
m0 ‘ _.U

Wmfimfi N —

a 6
6

6

117
However, the structures of several niobates containing the oxalate
ligand show Nb-O bond distances ranging from 2.07 to 2.16 4.55’56
The structure of [NbOC12(OC2H5)(bipyridyl)] reveals a suprisingly short
Nb-O (ethoxy) bond length of 1.87 3.54 To account for this, the
authors suggest the presence of considerable double bond character for
this bond. The niobyl, Nb=0 distance is 1.71 X in the molecule and
varies from 1.66 to 1.71 A in other Nb=0 containing structures.55’56
The average Nb-O distance of 2.13 A for Nb(DPM)4 compares favorably
with the above Nb-O single bond distances.

It is of interest to consider the possible reasons why Nb(DPM)4
adopts a D4 square antiprismatic configuration rather than one of the
two D2 dodecahedral molecular arrangements. Qualitatively, one might
predict that the D2(aabb) stereoisomer would be least likely to be the
coordination polyhedron for Nb(DPM)4. Such a configuration would
require the four identical bidentate DPM ligands to span polyhedral
edges differing by 252 (see Table XIV). Hoard and Silverton,3a in
fact, rule out the D2(aabb), C1(abmg), C2(mmgg) dodecahedra and the
C2(llss) square antiprism from consideration as possible stereoisomers
for neutral tetrakis bidentate chelates on the basis that the related
isomers with equivalent edges can better simultaneously minimize the
effects of both closed-shell repulsions and ring constraints. However,
as mentioned above, the polyhedron which best describes the structure
of Ho(DPM)3(4-Pic)247 is based on a C2(llss) square antiprism in which
a diketonate ligand spanningau11.edge is substituted by four picoline
ligands. Although this is not a tetrakis chelate, two of the DPM

ligands span 3 edges and one apans an 1 edge. To add further insight

into the prediction of eight-coordinate stereochemistries, Kepert57

118
extended Hoard and Silverton's38 ligand-ligand repulsion energy
calculations for eight monodentate ligands and showed that the potential
energy minima corresponding to the square antiprism and the dodecahedron
are very similar and that these stereochemistries are easy to distort.
Further calculations by Blight and Kepert58 showed that a potential
energy barrier between these stereochemistries does not exist, as

2’4’59 and therefore, in the absence of other stereo-

earlier assumed,
chemically-directing forces, there may be a continuous ligand movement,
creating a fluxional structure. More recently, Blight and Kepert have
extended their ligand-ligand repulsion energy calculations to eight-
coordinate complexes with four bidentate ligands.60 The relative
stabilities of the various stereoisomers were calculated as a function
of the "normalized" ligand bite i.e., the distance between the two
oxygens of the ligand divided by the metal-oxygen bond length. For
bites of 1.20 and 1.25, separate minima on the calculated potential

energy surfaces occur for the D and D4 square antiprisms. The D

2 2
dodecahedron appears as a saddle between these two stereoisomers with

a slightly higher energy. Consequently, the authors note that the
similar energies of these three stereochemistries make a prediction of
a given isomer impossible. Additional energy terms such as crystal
field stabilization, covalent o bonding, D bonding, and crystal

packing or solvation forces become important in determining the stereo-
chemistry. It is relevant to note that the ACAC bite in the Zr(ACAC)4
structure3b is 1.22 and the observed D2(ssss) stereochemistry is
consistent with the above predictions. As the bite of the ligand is

increased to 1.30, a single minimum corresponding to a D4 antiprism

appears on the potential energy surface. The authors state that ligands

119
with such a large bite would not be expected to form discrete eight-
coordinate chelates since the ligand-ligand repulsion would be lowered
if the ligands bridged different metal atoms to form a polymeric
structure. This is the reason, the authors summarize, that molecules
with this stereochemistry have not been observed. The bite of both
molecules in the asymmetric unit of the Nb(DPM)4 structure is 1.28.
Consequently, the observed D4 stereochemistry is again consistent with
Blight and Kepert's theoretical prediction. However, the ligand-ligand
repulsion does not appear sufficiently important to cause the compound
to adOpt a polymeric structure.

D. The Stereochemistry of Nb(DPM)4 in Solution

The stereochemistry of Nb(DPM)4 in solution was investigated
by means of electronic absorption spectrophotometry and ear spectroscOpy.
In both cases the same stereochemical assignment was implied.

The electronic absorption spectrum of Nb(DPM)4 in dichloromethane
solution is shown in Figure 23. Table XVI lists the absorption maxima
and the corresponding molar absorptivities. The qualitative features
of the spectrum include a broad absorption at 17.8 kK with a broad
shoulder at 15.4 kK and a sharper asymmetric band at 24.0 kK. The band
which appears off scale in Figure 23 is one of two bands in the ultra-
violet region at 32.0 (shoulder) and 35.0 kK. Deconvolution of the
spectrum results in two sets of bands containing either 4 or 5 bands
between 33.3 and 12.5 kK. Upon aging, the solution becomes pale yellow
(almost colorless due to dilution), and a concomitant decay of the
spectrum in the 33.3 to 12.5 kK region occurs until only the two bands

at 32.0 and 35.0 kK remain. This time dependence parallels the

 

120

 

 

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mo Eduuo0om coauouomom oficouu00H0 0nu mo aoww0u 0Hnfimfi> 0:9

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121

 

 

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122

Table XVI

UV-Visible Bands of Nb(DPM)4 in Dichloromethane (2.83 x 10'85)

Experimental:

Resolved:
(dashed lines)§

Resolved:
(dotted lines)§

Charge transfer:

650
561
416

680
550
415
387

705
655
545
415
387

312
286

Esz
15.4

17.8
24.0

-M-1 x 10-2

 

é-Dotted and dashed lines of resolved spectrum shown

in Figure 23.

123
conductivity observations discussed above (see p. 69) and again is
believed to be due to oxidation, possibly accompanied by hydrolysis.
Thus, the bands in the visible region may be due to transitions
involving the single d electron of the Nb in the +4 oxidation state,
but the two bands in the ultraviolet region are due to ligand charge
transfer. The validity of the latter assignment was confirmed by
observing the identical bands at 32.0 and 35.0 kK for a dichloromethane
solution of Zr(DPM)4.

There are three possibilities for assigning the bands in the
visible region: the bands may be due to (1) d-d transitions, (2) metal
to ligand charge transfer, and, (3) ligand to metal charge transfer.

In view of the large difference in intensities between the two bands at
14.2 and 15.3 kK (e = 280 and 636 cm7¥Mfl, respectively) as estimated
from the "dashed lines" in Figure 23 and the three bands at 18.4, 24.1,
and 25.8 kK (e = 2000, 1890, and 1620, respectively) as judged from

the deconvoluted spectrum in Figure 23, it is tempting to assign the
two low energy bands to d-d transitions. Figure 24 shows the crystal

61’62 As the eight

field splitting diagram for a D4d square antiprism.
monodentate ligands of D4d square antiprism are replaced by four

bidentate ligands, the symmetry is lowered to D and the degeneracy

4
of the E2 level is removed. Consequently, three d-d transitions would
be predicted. The observation of only two bands may be due to spectral
deconvolution inaccuracies or to a non-detectable energy difference
between the B2 and B1 energy levels. Deutscher and Kepert11b were
unable to assign any of the observed bands in the UV-visihle spectra

of several tetrakis diketonates to d-d transitions. However, the

above authors do make d-d assignments for three weak bands at 9.8, 12.8

124

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125

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126
(shoulder at 14.7), and 17.5 kK for the dodecahedral NbC14(C2H5 diars)2
in toluene. Agreement with the theoretically predicted number of
transitions for a dodecahedron (see Figure 24) is cited but the
appearance of shoulders at 14.7 and 23 kK is not explained. The bands
of lowest intensity in Nb(DPM)4 at 14.2 kK and 15.3 appear to be the
most reasonable candidates for assignment as d-d transitions, even
though the molar absorptivities are unusually high. However, bands of
unusually high intensity for d-d transitions have been assigned previously
for several tetrakis(8-quinolinolato)tungsten(IV) chelates in benzene

63,64

solution. Bands at 9.9 (e = 500) and 11.2 RX (6 = 450), for

example, have been assigned for both W(QCl and W(QBr (halogen

2)4
substitution at the 5,7 positions of the 8-quinolinol).

2’4

The remaining bands in Nb(DPM)4 at 18.4, 24.1, and 25.8 kK are
presumed to be charge transfer bands on the basis of intensity. An
attempt to make a specific assignment in terms of direction of the
transfer was hampered by the absence of consistent data on analogous
Nb(IV) chelates. It is probable that the transitions are due to ligand
to metal charge transfer in view of the electron-rich ligand N orbitals
and the high positive charge on the metal atom. An experiment that may
confirm this assignment would be to prepare, if possible, the trifluoro-
and hexafluoro acelylacetonate analogs of the DPM complex and look for
the expected high energy shift in the transitions as a function of
increasing fluorination. Deutscher and Kepert11b assign a band at 24.0 kK
(e = 1200) to a d to N *

l;
a n3 to d transition for Nb(ACAC)4 in toluene. However, the band at

transition and a band at 19.4 kK (e = 890) to

24 kK is assigned to a N3 to d transition in a subsequent discussion

in the publication. In spite of this confusion, the assignment of the

127
three bands between 18.4 and 25.8 kK in Nb(DPM)4 to charge transfer
transitions involving the Nb atom and the DPM ligands is reasonable.
The magnetic circular dichroism spectrum shown in Figure 25 was
recorded in an effort to confirm the deconvolution of the electronic

* With the exception of a shoulder at 23.6 kK,

absorption spectrum.
no new additional bands were observed. Thus it appears that the
deconvoluted spectrum represented by the dashed lines is the appropriate
choice, as was assumed in the above discussion (see Figure 23).

In an attempt to correlate the solid state stereochemistry with the
stereochemistry in solution, an electronic absorption spectrum of a mull
of Nb(DPM)4 was recorded. The spectrum is identical to the solution
spectrum both in terms of relative band intensities and band energies.
Thus, this evidence suggests that the complex retains a square anti-
prismatic stereochemistry in solution.

To test this hypothesis, an esr study of Nb(DPM)4 was undertaken.
The room temperature esr spectrum of the complex in hexane is shown
in Figure 26. Ten well-resolved nuclear hyperfine components are

93Nb). The anisotropic components

observed, as expected (I = 9/2, 100%
are observed in the hexane glass spectrum shown in Figure 27. The
isotropic and anisotropic g values (<g>, gll, gi) and the coupling
constants (<g>, All, and Al) were calculated with the aid of second

order corrections, since the high field approximation for determination

 

# The author wishes to acknowledge Professor C. Djerassi, Stanford
University, for recording the spectrum.

128

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129

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134
of g values was precluded by the rather large magnitude of the hyperfine
splittings6S (see Table XVII and XVIII). The room temperature spectrum
yielded <g> and <a>,and g1, gll, Al, and All were obtained from the
hexane glass spectrum. Only five of the ten possible parallel compo-
nents were resolved. Consequently, the positions of the third and
eighth, and fifth and sixth lines were used to determine All and gll.
The experimentally-observed parameters are tabulated and compared to
"calculated" parallel g and A values which were obtained by substituting
the experimental perpendicular and isotropic values into the following

equations:
a 3 — 2
8 I I <8) 8 I

A '-'-' - 2
II 3<a> Al

The experimental anisotropic values were substituted into the above
equations to obtain the "calculated" <g> and <a> parameters.
Theoretical calculations of ear parameters for a D2d dodecahedron
and D4d square antiprism have shown that gll < gl and AII >.Ai for a
dodecahedron and $1.< gll = 2.0023 and All < Al for a square

antiprism.61’67

The anisotrOpic parameters for Nb(DPM)4 show that

g1 = 1.928 < 8" = 1.997 and All - $2.70 < Al.= 141.16. It is evident,
therefore, that a square antiprismatic configuration is the correct
choice for the stereochemistry in hexane solution. The identical
spectrum.was obtained in dichloromethane at room temperature but the
parallel components were not resolvable from the glass spectrum due to
a solvent line-broadening effect which apparently has decreased the

spin-lattice relaxation time.66

135

Table XVII
Second Order Correction Equations For

Calculation of g Values65

 

 

For resonance, hv = gBHo
<a> 2
For <g>, Ho = Hm + <a>mI-+ 2H0 [ I(I+1) - mI ]
2
Al 2
For g“, H0=Hm+AIImI+-2-fi—[I(I+l)-ml]
0
A1? + AIIZ 2
For gi, Ho = Hm +AlmI + 4H [ I(I+1) - mI ]
0

Where Hm = the magnetic field position of the ESR line due to

the nuclear spin quantum number, m , v is the klystron frequency

I
and <a>, All, and Al are the hyperfine coupling constants.

136

Table XVIII

ESR Parameters For Nb(DPM)4

<g> - 1.95073 <g>(calc ) = 1.9508
<a> = 109.9 83 <a>(calc ) = 111.6 0
= —b— =
gll 1.9967 gll<ca1c.) 1.9965
gi = 1.927831
Al = 141.1-11
: h =
All 52.7 G A|I(calc.) 47.4 G

a
Measured in hexane at room temperature.

Measured in hexane at 77°K

137

The ear spectra of the Nb(DPM)4 powder at room temperature and
77°K are shown in Figures 28a and 28b. At least 14 lines are visible
which may be a result of two sets of 10 lines, some of which are over-
lapping. This would imply the presence of two magnetically-nonequivalent
Nb sites as is expected from the observation of two Nb(DPM)4 molecules
in the asymmetric unit of the unit cell.

To further confirm the postulation of a square antiprismatic
stereochemistry in solution, a Zr(DPM)4 host was dOped with Nb(DPM)4 by
dissolving both complexes in hexane and evaporating the solution to
dryness. Zr(DPM)4 is expected to adopt an antiprismatic configuration
based on the prediction of Blight and Kepert60 and the fact that
Zr(A.CAC)4 is known to be antiprismatic.3b The ear spectrum of the
doped powder at 77°K is shown in Figure 29; the spectrum is identical
to the hexane glass spectrum of Nb(DPM)4 (see Figure 27). To be
meaningful, an experiment of the above type is usually contingent
upon the host being isomorphous with the paramagnetic solute; otherwise
a distortion may occur in the structure of the solute when it occupies
lattice points of the host. However, in the above case, the question
of isomorphism is less critical since positive evidence was obtained
in that gll > g1 is consistent with a square antiprismatic geometry
and not a dodecahedral structure. Powder diffraction data were compared
for Zr(DPM)4 and Nb(DPM)4 as shown in Table XIX. The two patterns look
very similar, but small differences in the powder patterns make an
unequivocal statement regarding isomorphism impossible. The important
point, however, is that the doped powder and solution esr spectra were
identical and, therefore, consistent with the theoretical

predictions for a square antiprism, even though the symmetry in

 

 

138

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139

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140

 

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141

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144
Table XIX

X-Ray Powder Patterns for
Nb(DPM)4 and Zr(DPM)4

Zr (DPM)4 Nb(DPM)4
10.97-4- v.s.b‘ 10.43 v.s., bt
10.14 - v.8.
9.57 - v.3. 9.43 v.s., br
8.56 - s. 8.44 8., br
7. 3 - . 7.53 s.
6.59 _ 6.51 m.
6.40
6.17 w.
5.81 - v.w. 5.72 w.
5.51 - v.w. 5.38 v.w.
5.12 - v.w. 5.05 m.
4.95 - w.m.
4.81 - v.w. 4.87 w.
4.67 - m. 4.71 m.
4.52 - m. 4.58 v.w.
4.44 m.
4.27 - s. 4.29 m.
4.01 - w. 4.06 w.
3.76 - w. 3.86 w.
3.72 w.
3.41 - v.w. 3.51 v.w.
3.29 - v.w. 3.30 v.w.
3.18 - w.
3.15 - w. 3.16 v.w.
3.05 v.w.
2.95 v.w.
2.86 v.w.
2.32 - w.

0
a d-spacing in A units.

b Visual estimates of intensity with the following abbreviations
used: v.s. = very strong, s. = strong, m. = medium,
w. = weak, v.w. = very weak, br. = broad.

145
solution may be D2 or C2 rather than D4.
The question of retention of the solid state stereochemistry in
solution has been a widely-studied aspect of the chemistry of many
complexes and in particular, the Mo(V) and W(V) octacyano

2,58,61,67-69
system.

Emission spectral data from frozen powders and
solutions of lanthanide metal beta-diketonates has been presented as
evidence for the presence of the D4 antiprism.7O However, in both of
the above systems, the nature of the influence of cations and solvents
on the stereochemistry in solution is unclear and consequently, the
interpretation of the experimental observations is surrounded by

controversy.68’69’71

On the other hand, as described above, the
square antiprismatic polyhedral framework of Nb(DPM)4 .18 retained

in solution.

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64.

148

D. B. Copley, F. Fairbrother, and A. Thompson, J. Less. Com. Met.,
6, 256(1965).

 

D. B. Capley, F. Fairbrother, K. H. Grundy, and A. Thompson,
J. Less. Com. Met., 6, 407(1964).

 

R. C. Fay and R. N. Lowry, Inorg. Chem., 2, 2048(1970).

 

S. J. Lippard and 11 J. Russ, Inorg. Chem., 1, 1686(1968).

 

W. DeW. Horrocks, Jr., J. P. Sipe, III, and J. R. Luber, J. Am. Chem.
Soc., 22, 5258(1971).

 

C. S. Erasmus and J. C. A. Boeyens, J. Cryst. Mol. Struct., 2,
83(1971).

 

C. S. Erasmus and .L C. A. Boeyens, Acta. Cryst., B26, 1843(1970).

 

 

J. P. R. DeVilliers and J. C. A. Boeyens, Acta. Cryst., B27,
692(1971).

M. J. Bennet, F. A. Cotton, P. Legzdins, and S. J. Lippard, Inorg.
Chem., 2, 1770(1968).

F. A. Cotton and J. S. Wood, Inorg. Chem., 2, 245(1964).

 

F. A. Cotton and J. J. Wise, Inorg. Chem., 5, 1200(1966).

 

N. Galesic, B. Matkovic, M. Herceg, and M. Sljukic, J. Less. Com.
Met., 22, 234(1971).

 

G. Mathern and R. Weiss, Acta. Cryst., B27, 1610(1971).

 

G. Mathern and R. Weiss, ibid., Acta. Cryst., B27, 1572(1971).

 

 

D. L. Kepert, J. Chem. Soc., 4736(1965).

 

D. G. Blight and IL L. Kepert, Theor. Chim. Acta., 22, 51(1968).

 

J. L. Hoard, T. A. Hamor, and M. D. Click, J. Am. Chem. Soc.,
22, 3177(1968).

 

D. G. Blight and D. L. Kepert, Inorg. Chem., 22, 1556(1972).

 

B. R. McGarvey, Inorg. Chem., 2, 476(1966).

 

R. V. Parish and P. G. Perkins, J. Chem. Soc.,(A), 345(1967).

W. D. Bonds, Jr., and R. D. Archer, Inorg, Chem., 26, 2057(1971).

 

R. A. Pribush, University of Massachusetts, private communication.

65.

66.

67.

68.

69.

70.

71.

149

D. P. Johnson and R. D. Bereman, J. Inorg, Nucl. Chem., 26, 679(1972).

 

J. E. Wertz and J. R. Bolton, "Electron Spin Resonance", McGraw—Hill,
Inc-: New York, 1972, Chapter 9.

R. G. Hayes, J. Chem. Phys., 66, 2210(1966).

 

B. J. Corden, J. A. Cunningham and R. Eisenberg, Inorg, Chem., 2,
536(1970).

 

T. V. Long, 11, and G. A. Vernon, J. Am. Chem. Soc., 22, 1919(1971).
See also references therein.

 

(a) H. Samelson, V. A. BrOphy, C. Breecher, and A. Lempicki,
J. Chem. Phys., 62, 3998(1964). (b) Von E. Butter and W. Seifert,
Z. Anorg. Allg. Chem., 61, 384(1971).

M. O. Workman and J. H. Burns, Inorg. Chem., 2, 1542(1969).

 

APPENDIX A

Diketonate Ligand Abbreviations

APPENDIX A

Diketonate Ligand Abbreviations

 

 

Abbreviation Trivial Name R COCHCO R
R1 R2
1 2
ACAC acetylacetonate CH3 CH3
BZAC benzoylacetonate C6HS CH3
BTFA benzoyltrifluoroacetonate C6H5 CF3
DBM dibenzoylmethanate C6HS C6H5
DPM dipivaloylmethanate _E-CAH9 2-C4H9
S
TTFA thenoyltrifluoroacetonate H il CF3
Tp tropolonate ——-——

APPENDIX B

Observed and Calculated Structure Factors (multiplied

by 10 and using a scale factor of 0.9453)

APPmflHX B
Observed and Calculated Structure Factors (multiplied

by 10 and using a scale factor of 0.9453)

H K FOBS FCAL H K FOBS FCAL H K F085 FCAL

9* L = 0 0%
0 2 335 358 4 3 1213 1184 8 4 521 551
0 3 131 62 4 4 556 514 8 5 106 149
0 4 425 395 4 5 159 188 8 6 388 317
0 5 104 49 4 6 270 307 8 7 610 577
0 6 181 253 4 7 717 709 8 8 171 162
0 7' 787 706 4 8 200 198 8 9 72 80
0 8 142 128 4 9 103 92 9 0 86 130
0 9 83 68 4 10 81 109 9 1 656 546
0 11 113 168 4 11 320 320 9 2 124 143
1 0 49 52 S 0 172 218 9 3 314 303
1 1 2649 2682 5 1 983 769 9 4 53 78
1 2 202 159 S 2 439 385 9 5 685 689
1 3 84 79 5 3 677 647 9 6 293 256
1 4 118 99 S 4 264 348 9 7 S8 85
1 5 bag 577 S 5 111 115 9 8 331 312
1 6 439 513 S 6 861 779 9 9 334 322
l 7 74 27 5 8 567 492 9 lo 134 143
1 8 459 499 5 9 153 137 10 0 1260 1207
1 9 53 117 5 10 95 89 10 1 62 135
1 10 67 31 6 0 206 257 10 3 326 250
2 0 3415 3602 6 1 176 257 10 4 701 694
2 1 113 175 6 2 198 221 10 5 143 142
2 2 193 168 6 3 141 133 10 6 311 285
2 3 930 944 6 4 102 133 10 7 422 389
2 4 72 221 6 5 260 325 10 8 186 157
2 5 123 131 6 6 150 49 11 0 61 75
2 6 519 522 6 7 890 863 11 1 741 742
2 7 683 617 6 8 244 248 11 3 488 468
2 8 74 75 6 9 101 106 11 4 138 144
2 9 135 141 6 10 120 118 11 5 306 274
2 11 96 90 6 11 318 287 11 6 328 320
3 0 263 274 7 0 52 151 11 8 186 184
3 1 332 411 7 l 239 227 11 9 168 186
3 2 1237 1060 7 P 515 406 11 10 91 97
3 3 330 421 7 3 226 213 12 0 709 7?3
3 4 287 285 7 4 150 100 12 1 115 108
3 5 724 630 7 S 190 185 12 2 237 2?4
3 6 667 617 7 6 607 603 12 3 100 116
3 7 73 53 7 8 604 564 12 4 606 598
3 3 340 342 7 9 219 211 12 9 149 l?l
3 9 55 70 7 10 144 141 12 6 142 144
3 10 138 124 8 0 679 687 12 7 202 179
4 0 640 677 8 1 141 80 12 8 95 90
4 1 1145 1001 8 2 71 50 13 1 ‘5“3 69’
4 2 497 475 8 3 280 269 l3 2 173 198

ii

*APPENDIX B (Cont'd)

H K F085 FCAL H K FOBS FCAL H K Fons FCAL

13 3 440 402 0 2 548 507 -3 7 343 304
13 4 172 140 o 3 89 104 3 7 241 284
13 5 435 389 0 4 212 155 -3 R 265 P70
13 6 137 163 0 5 663 630 3 R 351 361
13 8 148 133 o 6 325 377 -3 10 335 310
13 9 81 108 0 8 167 192 3 10 228 243
14 0 336 332 o 9 331 356 3 11 85 104
14 2 133 146 -1 1 2083 2101 -4 1 192 164
14 3 371 383 1 1 1626 1787 4 1 2007 1942
14 4 453 442 -1 2 382 309 -4 2 2131 1903
14 5 64 90 1 2 444 406 4 2 1343 1342
14 6 67 109 -1 3 630 487 -4 3 357 319
14 7 278 251 1 3 88 70 4 3 342 385
15 1 457 454 1 4 574 571 -4 4 508 469
15 2 177 165 -1 5 114 76 4 4 136 175
15 3 226 220 1 5 173 141 -4 5 389 352
15 4 319 334 -1 6 402 412 4 5 398 426
15 5 166 163 l 6 364 328 -4 6 53? 499
15 6 360 335 -1 7 420 416 4 6 142 183
15 7 93 81 1 7 345 319 -4 7 122 123
15 8 167 181 -1 8 293 278 —4 8 164 141
16 0 570 572 1 8 320 372 4 8 334 338
16 2 87 79 -1 10 197 160 —4 9 444 382
16 3 265 290 1 10 210 180 4 9 332 280
16 4 111 143 -2 1 291 312 -4 11 151 150
16 5 95 76 2 1 103 77 4 11 130 138
16 7 283 290 -2 2 839 647 -5 1 1130 903
17 0 66 111 2 2 266 262 5 1 861 781
17 1 482 447 -2 3 142 166 -S 2 97 100
17 3 115 125 2 3 625 661 5 2 136 126
17 4 225 246 -2 4 299 334 -5 3 1672 1379
17 5 151 145 2 4 48 91 5 3 718 676
17 6 215 237 -2 5 716 661 -5 4 440 427
18 0 538 543 2 5 447 444 S 4 718 673
18 3 277 275 -2 6 529 468 5 5 103 133
18 4 234 229 2 6 543 530 -S 6 707 724
18 6 119 109 -2 8 171 188 S 6 816 699
19 1 214 241 2 8 82 85 -S 7 461 462
19 2 191 184 -2 9 422 377 9 7 438 420
19 3 124 123 2 9 470 457 -S 8 517 483
19 4 109 135 -3 1 251 311 9 H 399 3RR
l9 9 218 232 3 1 925 886 -5 10 170 156
20 0 291 340 3 2 477 505 5 10 224 225
20 1 99 104 -3 3 1568 1577 -6 1 153 140
20 3 175 168 3 3 271 303 6 1 136 255
21 0 84 99 -3 4 252 343 -6 2 1234 1246
21 1 199 214 3 4 444 438 6 2 1170 1161
-3 5 169 157 —6 3 138 144

*8 L = 1 8* 3 5 140 155 6 3 89 117
-3 6 569 524 —6 4 93 142

0 1 478 461 3 6 483 419 6 4 272 285

iii

#—

0:313D~JNCDJMfl£‘bLJuJV~*~*~—iO~OJJmJFJ7fl X

334x133.nm»uwm~—ooacx3~a~tnmbw«\1m~

FOIS

567
1297
482
343
242
447
331
170
132
182
456
308
321
930
148
554
120
739
538
612
453
550

317
251
292
332
771
896
56
588
558
498
580
346
232
213
478
281
590
897
128
647
728
93
257
164
211
340
276
309
34?

FCAL

586
1273
400
297
239
433
350
15?
126
258
492
354
189
951
132
561
110
739
525
566
388
520
307
218
104
243
751
858
65
580
511
480
460
289
207
216
502
315
504
837
136
705
699
92
231
172
235
329
288
301
340

APPENDIX B (Cont'd)

H

q
9

K

g
q

~9 10
9 10

~10
10
~10
10
~10
10
~10
10
~10
10
~10
10
~10
10
~11
11
11
~11
11
~11
ll
11
~11
11
~11
11
~11
ll
11
~11
12
~12
12
~12
12
~12
12
~12
12
~12
12
~12
12
~12
12
~13
13

fl
wwcommoommbtwwmmv-vo000:1:~1~1oombbuwm~—~o~orma~o~mmt~buwmm

iv

F035 FCAL
228 217
95 H2
280 247
273 254
768 703
878 866
103 104
382 331
288 29?
209 P38
613 50?
566 493
236 218
285 P39
197 194
284 257
331 341
309 291
539 577
627 642
113 125
928 856
799 755
426 377
230 217
136 125
216 200
245 228
178 175
203 206
198 192
192 184
67 72
222 213
137 152
908 907
1061 995
78 60
84 65
278 262
259 260
472 465
429 395
179 172
137 125
135 117
213 188
210 191
248 233
420 416
392 411

H

13
~13
13
~13
13
13
~13
13
13
~13
13
~14
14
~14
14
~14
14
~14
14
14
14
~15
15
15
15
15
l5
15
~16
16
~16
~16
~16
16
16
~17
17
~17
17
~17
17
17
~17
17
~15}
18
~18
18
~18
1R
~18

K

UT?4‘UUNNO‘O‘U’IJ-‘4‘UUHHO‘U'IU'YDUNNmflc‘waF-‘CDO‘WUTbPUUNNQQNO‘O‘U'IDbUMN

FOIS FCAL

97 106
847 823
734 684
333 283
311 301
90 78
152 154
175 185
165 155
136 111
229 195
722 734
807 676
105 154
133 124
283 260
93 60
298 339
451 421
91 98
174 167
284 283
362 353
163 135
299 299
277 241
151 116
211 205
409 411
481 411
88 99
117 114
489 526
437 407
142 108
251 270
340 319
177 216
193 175
304 321
360 312
76 61
183 214
120 104
226 245
254 225
119 141
115 104
161 187
128 116
229 265

18
~18
~19

19
~19

19
~19

19
~20

20
~20
~21

{1%}

I I I I I I I
m,\),\)\).\,V1V—--——~H1—-—~Hr—HI—'~oCOocoooao

K

HJ-‘NNJ-‘J-‘UUH—‘O‘JI

'—

UNVHHCOOOOWGDO‘O‘WU'TbDUWNNF‘HOOGENO‘mbUNh-‘O

F085 FCAL
202 191
99 115
135 155
202 217
211 259
235 211
211 216
226 183
170 203
302 290
116 151
128 159
: 2 an»

3515 4147
315 359
58 179
160 209
513 587
237 204
318 349
488 471
94 100
73 S2
64 74
116 148
2069 2223
1709 1921
1669 1508
2504 2261
401 396
86 42
98 63
390 339
896 847
810 794
480 493
463 495
296 308
380 454
260 310
134 133
106 110
2957 3103
2052 2102
45 43
63 149
468 409
287 303
789 879

APPENDIX B (Cont'd)

H K FOBS'FCAL
2 3 854 983
-2 4 503 439
2 4 205 335
~2 5 125 174
2 5 161 190
-2 6 270 241
2 6 351 384
~2 7 555 564
2 7 660 635
-2 8 176 231
2 8 62 13
2 9 152 150
2 11 156 171
-3 O 366 338
3 0 135 131
~3 l 613 599
3 1 2126 1992
~3 2 887 723
3 2 1122 1063
-3 3 659 662
3 3 225 154
-3 4 110 178
3 4 282 268
-3 5 286 329
3 5 426 421
~3 6 670 623
3 6 524 544
-3 8 422 403
3 8 511 550
~3 9 200 164
3 9 67 40
~3 10 128 140
3 10 81 86
~4 0 507 484
4 0 1376 1182
~4 1 1594 1254
4 l 1010 964
-4 2 484 473
4 2 543 502
4 3 751 773
-4 4 638 616
4 4 84 156
-4 5 121 180
4 5 166 166
~4 6 606 513
~4 7 586 618
4 7 922 880
4 8 204 170
~4 9 111 117
4 9 131 12?
4 10 137 121

V

H

-4
4
-5
5
-5
5
-5
-5
5
-5
5
-5
5
-5
5
-5
-5
5
5
5
~6
6
-6
6
6
~6
6
~6
6
-6
6
-6
~6
6
-6
6
6
6
-6
6
7
-7
7
-7
7
-7
7
-7
7
-7
7

K

11
11
0

\OCDGNNO‘UWU‘FOUUNI-‘HOOOO@GNO‘O‘U'IWF6‘wwNI-‘HO

h—I-II-i
mun$~bcguunHv-—-o~——-o

F085 FCAL
296 282
251 279
162 112

58 71
572 354
550 575

1194 1155
655 574
194 271
155 169
579 547
578 570
217 189
450 409
812 780

87 100
609 509
425 438
186 231
152 140
254 282
131 151
333 315
189 277
512 468
609 466
495 540

86 94
526 526
156 161
241 238
794 737
982 941
681 667
194 175
173 168

85 60
171 174
326 287
245 250

67 76
257 375
933 810
484 460
633 546
250 172
294 359

69 141
479 504
589 579
214 228

 

H

-7

~7

-7

-7

~8

~8

-8

-8

~8
~8

~8

~8

-9
-9
-9
-9
-9
-9
-9
-9
~10
10
~10
10
~10

10
~10

K

pat—a
UNNHHOOOOOOWCDO‘O‘UTUWUUNNHI-OOWCDNNO‘O‘Lnt‘J-‘LJUNHHOOOOCOCDZDO‘O‘

-

F085 FCAL
757 691
353 377
706 681
260 239
107 89
327 328
119 120
161 166
982 815

1653 1596
99 82
212 204
223 234
91 104
407 398
200 119
977 898
73 71
386 424
192 190
711 666
578 538
168 163
250 241
72 58
264 256
733 706
1076 1028
211 244
832 735
341 329
304 327
718 602
403 453
397 359
424 388
436 430
195 215
121 107
288 282
100 118
119 93
1620 1699
795 749
94 144
62 37
154 125
165 194
304 338

APPENDIX B (Cont'd)

H

10
~10
10
~10
10
~10
10
~10
10
~10
10
10
~11
11
~11
11
~11
11
~11
~11
11
~11
11
~11
11
~11
11
~12
12
~12
~12
12
~12
12
~12
12
12
~12
12
~12
12
12
~13
~13
13
~13
13
~13
13

K

wUNN—‘HOCDNI‘IU‘O‘U'I‘P«L‘WUNNHOOOOCnmo‘O‘UTU‘bUUNNF‘HOWQNNO‘O‘U'I'JI“{PU

FOBS'FCAL H

501
869
559
120

87
180
281
329
380

95
218
102
647
599
240

68
657
297
346
442
574
249
355
166
225
107

94
750
328

90
111
219
199
119
648
694

80
186
163
222
294
154
101
555
406
137
113
554
296

v1

525 ~13
834 13
558 ~13

96 13

92 ~13
197 13
228 13
286 ~14
382 14
111 ~14
230 14
103 ~14
651 l“
559 ~14
272 14
149 14
615 14
322 14
350 ~15
401 15
512 ~15
236 15
337 ~15
163 15
211 ~15
116 15
102 ~15
718 15
327 ~15
112 ~15
136 15
217 ~16
229 16
109 16
624 ~16
623 16
84 ~16
194 16
183 16
214 ~16
304 16
133 -17
96 17
592 -17
366 17
256 ~17
135 17
592 ~17
244 17

K

.b£>ucgnHv-—-‘gq:hg~p.gLgn39<33~ogn¢nbggwrvn1~r~c>OCD~IOI>s‘wtdn;N<Dc>wcrO‘anc‘b

F085 FCAL
219 202
102 144
322 337
282 237
201 211
302 327
296 275
654 623
354 354
165 196
108 84
399 375

67 82
671 655
79 106
126 139
528 500
80 96
95 123
68 36
400 423
437 383
263 262
107 113
288 301
145 134
249 251
166 174
274 299
196 192
377 363
426 485
694 634
111 88
380 386
120 144
347 383

77 96
144 115
132 131
341 326
294 290
432 390
99 156
125 128
93 120
131 126
150 188
211 182

~17
17
~17
17
~18
18
18
18
~18
18
~18
18
~18
19
~19
19
~19
19
19
19
~19
~20
20
~20
20
~20
~20
~21
~21
~21

~—-—u—-—a.——1—OODOOOOOO

K

N-‘Owa—‘OOU‘§UNNHHOO4§¢UUV~OOOOWUT

r

UT§JQVN-~03®J1PJNH

F085 FCAL
157 170
276 240
188 192
175 166
388 364
540 554
140 143
107 98
186 223
276 243
163 198
254 224

95 102
76 118
174 185
354 367
148 186
152 138
123 123
130 125
209 218
156 175
507 496
98 93
81 113
189 220
181 208
80 109
118 160
160 186

= 3 {H}

296 323
1945 1799
30 78
178 266
1016 1028
350 328
94 76
476 492
88 82

1301 1332

1231 1204
252 297
320 296
183 257
68 74

1032 1022
221 236

APPENDIX B (Cont'd)

H

K

u—u—ou—I
-aoaow~1~zo~a~u1

oquuommbbwwmm-~oommowmmbbuuvm—

v11

F085 FCAL
90 116
382 417
362 383
267 308
109 100
224 222
299 313
237 248
248 273
64 92
279 299
169 213
2086 1888
1080 1055
171 260
120 242
400 392
305 321
574 530
985 1080
340 328
186 293
290 322
127 106
287 279
429 401
95 97
862 783
1157 1078
145 183
188 249
849 861
562 543
66 100
1123 981
58 113
302 356
399 361
573 588
326 354
336 332
352 331
98 71
229 226
185 185
122 148
87 104
2489 2248
454 461
1364 1233

H

7

K

~—
~000333‘3‘J‘1‘J196‘UN

gm ~
~

_o
HWWOOJD$©WW1§§UQNN~HOOommflfla‘mbbduwm—fl

Fons FCAL
1418 1315
445 437
344 312

40 49
267 234
844 827
659 604
150 204
141 134
182 193
374 366
211 207

73 93
123 130
123 158
735 611
202 172
292 282

90 109

1200 1114
864 912
120 64
877 829
303 316
408 395
564 550
333 263
484 442
158 113

59 55
259 251
344 347
529 534
194 269
704 691

1392 1358
287 216
361 366
209 204
251 201
452 445
752 755
798 730
228 205
118 134
411 426
178 206
158 151
177 243
1064 994

H

-7
7
-7
7
-7
7
-7
-7
7
-7
7
-7
7
7
-7
7
-8
8
~8
8
-8
-8
8
~8
8
~8
~8
8
-8
8
-9
9
9
-9
9
-9
9
-9
-9
9
-9
9
-9
9
9
—9
9
-10
10
-10

K

2
2
3
3
4
4
S
6
6

1
1

7
7
8
8
9
0
0
1
1
2
2
3
4
4
5
S
6
8
8
9
9
1
1
2
3
3
4
4
5
6
6
7
7
8
8
9
10
10
1
1
2

F085 FCAL
126 131
354 334
194 169

1122 1111
162 106
671 641
137 201
428 397
343 329
440 425
186 168
484 465

81 95
82 82
263 239
306 297
130 153
388 351
536 616
713 733
161 206
188 179
580 538
593 527
527 566
352 345
243 229
269 280
507 521
257 241
406 360
769 690
84 86
351 429
606 541
489 458
207 210
82 72
363 349
456 397
238 225
324 290
357 354
139 173
71 88
268 254
251 249
173 217
191 232
801 747

APPENDIX B (Cont'd)

H

10
~10
10

~10
10
~10
10
~10
10
10
~10
10
~11
11
11
~11
11
~11
11
11
~11
11
~11
11
~11
11
11
~11
~12
~12
12
~12
~12
12
~12
12
~12
12
12
~12
12
~13
13
13
~13
13
~13
13
13
~13

K

0019¢UUN~H~D~OGO‘O‘U'IUWbJ-‘UNNI-‘OOOENNO‘O‘UTDDUUNI-‘F'OOCDO‘O‘UTUTPéUUN

FOBS'FCAL
580 594
404 384

85 97
349 316
383 341
551 536
348 303
173 142
280 264
253 242
383 378
337 305
380 375
368 355
203 185
792 837
587 590
568 532

57 32
244 231
183 192
185 192
168 160
277 281
175 178
190 172

66 52
222 224

85 115
771 747
737 707
346 351
373 340
132 64
313 301
198 205
203 189
151 174
223 213
197 165
223 228
472 494
329 297

91 101
825 823
455 380
401 392
148 143
112 113
195 174

viii

H

13
13
13

-14
14

-14

-14
14

-14
14

-14
14
14

-14

-15
15

-15
15

-15
15

~15
15
15
16

~16
16
~16
16
~16
~16
16
16

-17
17

-17
17

-17
17
17

-17

-17
18

~18
18
18

~18
~18
~18

-19
19

K

"HomwaN—‘flomékwwwwO‘U'IUIkUUNNU-I‘NOOfibUUHfiomOOU‘W6‘4‘UNNQNO‘

F085 FCAL
300 312
299 280
235 233
688 768
581 567
193 221
321 313
118 116
283 295
444 428

99 144
92 103
170 175
149 110
418 470
347 332
746 745
255 265
396 444
291 280
177 182
253 250
202 190

70 119
380 375
422 384
118 101
167 150
242 288
377 421
220 245
170 157
244 242
350 342
282 295
223 199
247 267
260 245
78 78
181 207
98 91
103 98
252 245
313 315
70 82
121 151
254 267
125 107
155 152
318 327

H

~19

19
~19
~20
~20
~21

#
#

wh—wHHc—IHD—ic—u—dwr—u—t—t—voocccooOOOO

I I I I
NfUhJN--~*~

~2

K

hJ¢FU£‘ULJ

r

n-H
$6nc~§(gn}-—hvo<3c>o‘003®~dO‘OLDUW&(AUJNIU~'HCDC>-OGDNCfiU1bLJHJHCD

FOBS FCAL
180 205
143 133
135 156
192 225

96 115
235 277

: 4 fl”

1748 1523
155 129
190 219

97 115
902 903
286 338
277 280
170 188

72 103
112 161
184 206
511 496
588 551

1378 1304

1418 1274
61 168
572 565
125 103
70 189
528 496

1152 1234
722 673
347 304
400 455
86 104
283 261
397 404
226 239
108 148
131 148

1369 1439

1714 1572
179 123
268 275
412 398
214 239
435 521

1334 1248
603 548
308 259
289 309

APPENDIX B (Cont'd)

H

X

pup—p9

~038—hvo\OlDN‘QO‘OLHC‘b(JUJNWUF‘FH3CDCIO~OGDG‘QO‘OLHU1kflthNFUMHHCDOfiflh'O\Oaim'd~d3

’—

Fwy—l

F085

115
371
546
161
53
91
85
143
201
111
266
1854
958
203
326
341
349
470
788
204
322
429
54
499
453
221
57
96
1709
218
1159
172
468
356
152
859
770
145
232
490
215
722
789
92
64
148
225
212
118
639

ix

FCAL

159
487
559
202
92
96
70
136
211
175
253
1694
965
227
313
345
305
421
821
161
258
456
88
486
452
171
47
96
1541
192
1055
263
447
354
264
948
704
71
186
463
273
793
769
114
65
147
217
236
134
571

X

(>Q~Q~JOW3LHU1¢H§CJLJRHVI‘F'Gbo<3€>£>®£bd~0hflu1#‘btdLJfilfl

O‘OLflU1b-thUfUhJ~W~C>O

FOIS FCAL
323 408
857 916
362 377
394 388
197 198
591 586
845 812
116 126
173 173
510 544
523 500
244 272
172 193
125 141
158 151
204 152

1218 1205
375 487
704 657
304 256
410 395
313 356
389 402
838 885
622 564
127 127
165 162
711 725

60 83
740 704
535 436

74 104

73 64

99 129
140 140
276 276
182 212

75 67
319 294

1279 1224
1064 947
795 712
142 155
445 440
382 322
377 342

1004 946
212 220
374 299
451 465

I I I I I
ccocccocooocooooommmmmmmmmmmmmmmmququu I

pug—o

K F085 FCAL
8 459 420
8 78 78
9 300 299
0 150 162
O 123 126
0 522 532
0 2043 1834
1 253 175
1 171 174
2 238 248
3 707 757
3 205 257
4 419 435
4 799 757
5 123 122
6 350 377
7 662 624
7 210 169
8 90 86
8 285 285
9 76 54
0 75 33
0 163 163
1 632 601
1 712 715
2 448 449
2 89 113
3 232 272
3 218 281
4 343 337
4 80 127
5 524 487
5 507 515
6 495 484
6 387 348
7 70 91
8 419 415
8 138 156
9 105 114
9 98 124
0 142 133
0 1352 1340
0 665 716
1 120 163
1 177 245
2 192 204
3 632 560
3 153 212
4 502 463
4 665 658
5 148 113

APPENDIX B (Cont'd)

H

-10
10
-10
10
-10
10
10
10
-11
11
-11
ll
-11
11
-11
ll
-11
-11
11
-11
11
'11
ll
-12
12
‘12
12
-12
12
'12
12
12
'12
12
'12
12
12
~13
13
'13
13
~13
~13
13
~13
-13
'13
13
l3
-14
14

K

0933‘OUI¢UUNH~OOZDNN3QU1b¢UUNNOO-rmO‘O‘U'IU1$‘WUNNHHOOOGJNNO‘O‘O‘O‘

F085

115
169
115
169
356
170
189
94
126
134
638
530
268
251
308
148
103
611
559
215
291
222
306
735
646
74
199
660
230
593
347
74
185
124
241
578
127
73
98
482
438
323
403
86
209
338
233
495
339
728
465

X

FCAL

91
179
91
179
341
221
171
102
146
116
615
525
232
226
29?
185
98
567
503
183
296
206
284
748
588
85
199
613
191
520
248
79
195
157
234
584
125
109
60
447
426
309
433
118
210
347
218
485
349
705
454

H

-14
-14
14
-14
-14
-14
14
14
15
-15
15
-15
-15
15
-15
-15
15
15
--16
16
-16
~16
-16
16
-16
16
-16
16
17
~17
17
-17
17
17
~17
-17
17
-17
-18
18
-18
-18
18
-18
-19
19
-19
-19
-19
~20
-20

K

U'UO‘U‘NHHU‘Jv‘bUOOO‘U‘IJIl-‘UNNHHOO‘O‘6‘bUUNHOOO‘U‘U‘bMUNF-‘HONO‘O‘vI-‘UNNF‘

FOIS FCAL
161 197
139 138
220 204
360 365
604 590
145 142
194 184
S72 S68

76 81
382 363
356 34?
196 190
289 281
142 144
158 147
345 381
134 127
25? 277
481 544
482 459

76 85
117 99
230 269
154 136
448 474
290 251
169 138
177 161

86 106
189 189
291 315

89 97
134 104
165 151
113 131
313 329
256 242
117 106
258 251
516 561
109 148
186 250
179 190
109 116
169 166
394 391

81 111
224 235
135 161
111 143
140 172

APPENDIX B (Cont'd)

H K FOIS FCAL H K F085 FCAL H K P085 FCAL

-20 4 209 227 2 11 143 145 5 9 89 81
-21 2 117 131 -3 1 1067 1063 -5 10 335 336
~21 3 102 118 3 1 381 434 5 10 259 240
3 2 197 231 -6 1 240 331

68 L = 5 44 —3 3 808 767 6 1 556 503
3 3 989 1024 -6 2 1078 972

0 1 156 168 -3 4 166 171 6 2 1173 1193
0 2 292 447 3 4 1333 1332 6 3 74 02
o 3 85 131 -3 5 264 270 -6 4 609 604
o 4 469 453 3 5 129 158 6 4 350 309
0 5 748 740 -3 6 211 267 -6 5 240 238
0 6 255 268 3 6 281 282 6 5 541 598
0 8 138 141 -3 7 501 528 -6 6 564 566
0 9 599 607 3 7 238 199 6 6 140 137
0 11 134 159 -3 8 289 302 -6 8 94 81
-1 1 884 833 3 8 268 276 6 8 162 183
1 1 832 729 -3 10 205 214 -6 9 295 302
1 2 186 154 3 10 272 273 6 9 201 167
-1 3 131 260 -3 11 110 127 6 10 66 72
1 3 251 332 -4 1 537 497 -6 11 112 139
-1 4 495 486 4 1 283 408 -7 1 566 599
1 4 1310 1194 —4 2 1260 1150 7 1 1031 963
-1 5 271 296 4 2 1541 1442 -7 2 470 422
1 5 168 214 4 3 344 366 7 2 150 116
-1 6 236 273 -4 4 359 341 -7 3 793 904
1 6 222 280 4 4 79 82 7 3 992 939
-1 7 160 208 4 S 687 670 -7 4 457 467
1 7 98 89 -4 6 473 485 7 4 541 523
-l 8 281 313 4 6 370 374 -7 5 162 143
1 8 310 319 -4 8 244 247 7 5 119 124
1 9 82 98 4 8 84 103 -7 6 110 88
-l 10 295 375 —4 9 214 213 7 6 304 274
1 10 29? 349 4 9 243 228 -7 7 337 334
-? l 170 137 -4 11 111 131 -7 8 296 293
2 l 270 207 -5 1 127 126 7 8 62 22
-? 2 943 979 5 1 217 299 -7 10 329 327
2 2 923 1030 -5 2 228 268 7 10 206 171
-2 3 186 100 5 2 47 92 -8 1 519 426
2 ‘3 322 363 -5 3 963 1015 8 1 187 154
-2 4 550 S61 5 3 1160 1159 -8 2 286 295
2 4 256 261 -5 4 316 350 8 2 683 719
-2 5 436 372 5 4 753 724 -8 3 266 210
2 5 692 667 -5 5 205 185 8 3 119 102
—2 6 252 293 5 5 53 43 —8 4 425 446
2 6 331 296 -5 6 102 165 8 4 501 494
-2 7 81 105 5 6 180 220 -8 5 399 383
-2 8 249 274 -5 7 545 541 8 5 773 783
-2 9 375 396 5 7 103 155 -8 6 191 218
2 9 389 373 -5 8 235 188 8 7 103 103
-2 11 122 146 5 8 84 72 -8 8 92, 124

xi

H

I II I I
0101001010106me

III I I III II I I I I I I I I
wawwwwwuwwwwv—n—at—IHHHHI—nwwu~11-ao—v—ot-at-vt-‘HI I I I
mmwr-o—Ht—u—u—o—nwwo—Ho—vv-HOOOOOOOOCOO00000000101000

oquqoombbuumwv—oom

p—a

H
Nwommuwoombwumut—ocmuoomm59wwmmww

FOBS FCAL
212 196
383 398
325 304
763 713
540 559

71 176

98 49
646 680
720 709
340 341

71 92
372 337
318 317
306 245
169 131
284 299

65 67
260 248
210 287
127 97
554 560
456 488
516 494
251 234
132 151
551 507
345 381
226 218
267 270
206 233
109 111
130 130
375 352
310 292
632 664
408 376
77 109
286 261
390 351
406 396
140 149
223 220
250 275
182 158
356 339
206 200
225 208
206 212
136 171
710 724

H

12
-12
-12

12
-12

12
-12

12

12
-12
-13

13
-13

13
-13

13
-13

13
-13

13

13
-14
-14

14
~14
-14
-14

14
-14

14
-14
-15

15
-15

15
-15

15

15

15
-16
~16

16
~16

16
~16
-16

16
-16
-17

17

Ho—ommeuumm—omabwwwwomommbwmm-loa~m¢uumm-omoommkbum

xii

APPENDIX B (Cont'd)

F085 FCAL H
366 358 ~17
474 450 17
309 297 ~17

63 62 17
231 187 -17
94 105 -18
178 178 -18
304 311 18
157 183 -18
239 216 -18
384 404 -18
189 174 —19
121 150 -19
84 96 -19
643 629 -19
221 182 -20
441 47S -20
75 90 -20
127 123 -21
277 272
383 398 *9
182 220
698 691 0
342 342 o
277 286 0
326 317 o
309 272 0
138 144 o
146 146 o
242 219 0
154 138 0
336 342 0
203 197 0
723 730 0
342 329 -1
385 422 1
109 108 _1
118 144 l
137 162 -1
143 143 1
417 401 -l
340 334 l
95 101 -1
102 83 1
286 307 -1
156 173 1
125 147 '1
167 169 l
237 235 -1
294 299 1

U'J'II-‘Nibwh-‘O‘GJ-‘NNF‘O‘J-‘I-‘QU

I"

hunt-i

(1)000me¢UUNNHHOO~O¢J®NOW¢UN~O

93
53
69
474

1290

77
271
273

79
139

61
305
223
213
538
259

167
229
483
481
231
345
613
623
337
274
296
300

F085 FCAL
345 358
211 220
159 193
108 123
120 125

78 99
241 256
301 318
110 130
209 227
101 106
164 153
202 228
120 129

89 104
252 282

97 93
165 201
261 301

6 #8

179
123
177
458

1119

164
281
307
117
181
86
333
281
162
401
255
352
261
568
536
228
329
646
737
362
266
326
264

K

~—
UUNNV-‘HOOOOOOQmO‘O‘mU‘4‘PUUNNHF'OHOOW‘INO‘O‘U'IU'I“bww'VNI-‘HOOOOOO

F085 FCAL
96 73
146 178
126 166
136 165
897 780
228 390
239 252
45 127
106 156
85 125
192 185
1208 1203
1532 1454
452‘ 533
161 231
182 225
188 194
330 324
292 309
435 458
167 160
102 108
81 122
219 256
140 186
737 732
392 357
406 493
381 357
312 395
269 302
89 71
405 402
796 794
323 315
389 420
305 293
260 309
304 293
138 122
63 44
101 113
107 121
220 367
890 1013
282 301
272 248
315 301
400 338
282 312
698 705

APPENDIX B (Cont'd)

H

K

#fi

NHHOOONNG‘3‘UIPbUUNN—‘HOOOOWOO‘O‘U’IW“#‘UUNN—‘HOOHOOCDWNNO‘O‘U‘b?

FOBS'FCAL
1027 1033
167 231
135 166
282 276
282 285
581 571
451 454
177 165
99 69
71 97
74 98
191 204
87 95
127 104
181 322
1356 1287
634 607
46 49
552 572
297 256
216 219
299 246
758 720
416 372
301 337
292 290
243 257
232 269
92 70
151 145
98 171
1944 1721
534 545
136 106
309 291
403 366
341 332
133 127
892 851
636 613
134 133
263 271
64 99
452 397
179 119
91 103
227 192
78 168
778 756
922 880
1004

1039

xiii

H K

I
*1
0—0

-9

I
0000

II I I I
00101010000
Dd

OOOGO‘O‘U'IUI“(PUNN—‘HOOO‘OOQNNO‘O‘mlb‘bUUNNHt—OOOOOOWQO‘O‘mmbbUUN

F085 FCAL
61 106
363 395
352 330
124 136
239 222
626 627
555 550
84 89
450 395
70 58
221 201
82 110
217 213
90 134
149 158
1532 1521
722 827
521 531
69 95
93 87
203 190
879 787
333 358
793 774
671 696
228 210
357 354
78 72
467 434
126 116
87 106
70 83
93 54
85 77
178 228
108 99
798 791
432 478
1061 1063
372 332
263 233
442 504
206 191
457 472
634 596
330 266
211 201
331 326
178 157
151 129
134 121

 

ill..- I. l
l

H

-10
10
-10
~10
10
~10
10
-10
10
~10
10
-10
10
-10
10
10
~10
-1l
'11
11
-11
11
11
-11
11
-11
11
-11
11
11
-11
11
-12
12
-12
12
-12
12
-12
12
-12
12
12
-12
12
-12
12
12
-13
-13

K

Homqqo3mb¢uumm—~oommqoammbbummw—tcomqqaammbbuammwoo

F085 FCAL
913 801
846 861
221 251

96 130
105 99
811 746
309 321
275 239
491 437
132 107
184 166
288 252

96 88
423 422
181 230
100 100
108 113

92 138
612 626
463 411
593 612
138 136
124 143

86 98

77 71
533 522
187 213
253 204
214 237
140 126
304 284
330 319
607 622
549 528

78 76

85 117
200 220

69 60
652 652
144 175
478 436

67 60
105 97
124 122
146 149
210 234
562 591

78 100
124 110
495 529

APPENDIX B (Cont'd)

H

13
-13
13
-13
-13
-13
13
-13
13
-13
-14
14
-14
14
--14
14
-14
14
-14
14
-14
14
-14
-15
-15
15
-15
15
-15
15
-15
15
-15
-16
16
-16
16
--16
16
~16
-16
17
-17
17
-17
--17
17
-17
~18
18

K

oomuwwwwo~10~54~m~aommmuum-~o~103~bbwumw-ooma~o~mmbwmm~

FOBS'FCAL
340 324
374 325
204 215
228 229
156 164
377 373

70 77
157 163
344 324
215 175
410 410
402 432
161 198

72 83
137 150
166 157
240 227
219 218
459 435
172 172
152 160
196 173
152 140

87 39
372 389
377 376
123 159
183 183
251 264
123 96
403 423
246 207
117 104
373 390
419 467
134 165
104 107
382 415
262 276
216 225
107 93

79 89
223 213
314 339

77 67
126 158
102 114
420 448
329 310
437 471

xiv

H

-18
-18
~19
-19
-19
-19
-20
-20
-20
-20
-21

t
4

I
mmmmmmmmu—wt—IH—o—u-v—oI—Iu—r-Iu—oc—tr-Iu-oh-noccocccc

-2

K

I. UUI¢NOO~JID~U1¥>

Hfl
OfiO‘O‘WUIkl-‘UNNHOOQa‘INO‘O‘JIbkaNHF’OQO‘mI-‘NN—

F085 FCAL
257 267
121 138
165 165

81 109
188 205
161 190

91 50
103 139
191 175

82 87

83 90

z 7 OI»

92 104

66 175
492 486
555 542
387 471
305 311
105 117
396 418
272 307
121 134
165 145

1270 1225
1147 1116
707 690
927 779
110 110
345 416
286 295
194 194
202 180
237 241
230 259
359 436
358 424
179 176
492 540
1054 1025
631 561
474 435
205 276
516 649
276 284
180 204
324 377
176 167
407 426

Fit-l
m-ooommuuoommbauu-~—o X

v—nv—o
HOOQVNO‘O‘UIUI6‘4‘UUNH1O1OGJO‘O‘JIUI6‘6‘UN

F085 FCAL
348 346
477 484
410 359
158 170

41 96

1446 1526
905 921
227 151
564 581
226 237
111 129
333 316
212 208
315 315
181 198
176 218
230 238

64 85
308 295
283 288
256 367
490 480

1359 1301

1072 1040
257 247
426 431
255 279
153 192
405 434
235 247
220 219
283 320
230 223
323 271
757 744
108 103

1194 1188
702 699
266 287
322 360
128 106
174 212
275 266
172 181
444 436
126 188
190 214
294 279
111 100
561 566

APPENDIX B (Cont'd)

H
-6
-6
-6
-6

-6

-6

-7

-7

-7

-7

-7

-7

-7

-7
-8

-8

-8

—8

-8

-8

-8
-8

-9

-9

-9

-9

K
2
2
3
3
4
4
5
5
6
6
7
8
9
9
1
1
2
2
3
3
4
4
5
5
6
7
8
8
0
1
1
2
2
3
3
4
4
S
5
6
6
8
9
9
1
1
2
2
3
3

b

528

XV

FOBS FCAL
981 1009
822 853
220 254

48 S4
511 446
238 245
135 220
495 460
366 436
302 256

97 107
168 159
237 232
246 223
522 577
443 437
395 398

68 89
836 821
511 478
445 376
326 345
131 150
301 305
141 115
319 267
113 138

97 102
289 290
726 700
127 109
213 333
627 584
236 228

72 52
500 503
235 217
123 119
593 530
339 386
215 204

86 93
316 326
277 282
783 777
274 292
291 288

60 59
104 210
541 532

516

H

-9

-9
-9

~10
-10
10
-10
10
~10
10
-1O
10
~10
10
10
-10
-11
11
-ll
11
~11
11
-11
11
~11
11
-11
11
-11
11
12
-12
12
-12
12
'12
12
-12
12
-12
12
12
-12
~13
13
-13

K

Fons FCAL

447 437

66 85
174 122

93 127
189 157
275 293
100 73
233 238
108 137
204 211
421 409
265 255
182 201

82 63
332 321
349 333
340 356
312 322
201 225
161 132
319 307
469 471
306 264
168 149
339 307
443 474
365 333
118 108
133 127
255 206
269 284
105 121
268 252
229 215
172 181
196 209
690 732
368 341
297 310
154 153
124 127
181 192
449 415
198 183
163 178
313 293
84 89
222 225
318 316
208 238
525 494

H

l3
-l3
~13
13
'13
-13
’14
14
~14
14
'14
'14
14
-14
'14
14
-15
15
'15
15
-15
15
-15
-15
~16
'16
16
~16
~16
~16
-17
17
~17
“17
'17
-18
-18
'18
~18
-18
-19
-19
~19
-20
-20
-21

*1}

K

(a)bNfiUHO‘UIJ-‘NHNO‘UHHO‘kwm'V—‘mslmkUUHHOOW¢¢JNNHHO~JQO¢W

I"

O

FOBS FCAL
235 246
419 420
130 150
168 165
126 138
182 172
105 131

73 131
684 659
383 341
192 188
224 238
132 132
274 275
158 173
248 245
222 203
205 203
391 368
262 277
140 113
120 129
198 181
102 92
185 231
418 413
262 282

99 111
247 278
278 289
205 205
143 186
302 338
83 87
111 117
164 198
231 263
179 187
142 153
89 147
148 154
264 287
115 120
251 297
101 109
248 286

= 8 {H}
249 178

APPENDIX B (Cont'd)

H

1 1 1 1 1 1 1 1
uuuuwmmmmmmmmmmmmmmmmm----------°°°°°°°°°

K

1—1—
HHOOOONNO‘O‘UIU‘IJP#UUNNHHOOOOOQQNO‘O‘U‘IU‘I-‘bUUNNI-‘HOO omuombum—v

FOBS'FCAL
119 56
241 220
690 660
891 881

77 111
289 307
370 394

74 65

84 55
126 195
133 222
326 337
291 265
352 333
154 90
837 803
587 582
305 356

98 106
354 477
433 553
415 396
396 306

56 67
209 228
210 204

96 112
144 193
157 197
341 264
367 324
301 324
237 256
157 127

66 89
276 314
457 392
944 848
666 645

98 110
110 191
234 207
244 209
341 309
270 273
119 123

79 98
190 160
532 486
168 206

374»

351

xvi

H

K

pup-

NWF‘OOOwG‘O‘mWUUNNHF‘OOOGQNQO‘O‘U’I“?UUNNF‘F‘OOOOOOQO‘O‘WLJ'I8‘UUNN

F085 FCAL
494 419
271 340
734 700
434 418

76 117
342 364
421 408
371 420
285 296
114 121
252 237

59 50
118 127
106 131
419 500
926 899

65 70

98 161
238 262
176 188
129 163
278 300
687 714
707 668
133 176
153 193
189 166
333 317
191 192
179 180

99 120

74 71
173 144
315 261
850 838
978 967
529 513
577 539
270 240
245 252
483 508
555 569
362 361
176 157
173 217
203 173

1459 1433
1061 1024
454 436
401 394
384 408

H

6
-6
6
-6
6
-6
-6
6
-6
6
-6
6
-7

K

-oaooo~1~10~o~mbbyummu—u—ooommwoammbbuumm—u—acooqdwombbuum

F085 FCAL
228 209
577 605
285 300
655 605
505 518
115 139
124 149
243 269
230 210
103' 115
124 109

76 91
188 195
83 58
974 934
722 728
973 988
684 626
304 306
189 228
143 153
196 189
566 631
655 635
171 192
176 142
62 58
187 226
175 159
107 137

1853 1706
778 849
620 525
288 260
123 165
265 224
676 664
434 453
696 676
530 513
142 130
332 351
215 219
159 91

82 93
163 162
85 97
68 119
720 719
613 579

APPENDIX B (Cont'd)

H K F085 FCAL

-9
9
-9
9
-9

95

-9
9
-9
9
-9
-9
9
-9
~10
10
10
'10
10
-10
10
‘10
10
10
~10
10
'10
10
-10
~10
-11
11
-11
ll
-11
11
11
-11
11
'11
11
-ll
11
~11
-12
12
12
'12
12
'12

QNNJHOOJDO‘O‘UI'JIb#UNNHHOOOCDNNO‘OW¢¢JUNNF‘OOOZDQNIO‘J‘UIUIbbb-JUNN

545
287
145
133
374
209
566
461
152

97
118
217
228

97
747
682
164
159
167
465
268
276
245
238
357
116
310
275

88
104
152

92
509
260
284
207

82
269

88
298
137
277
169
296
299
169

87
260

65
323

xwii

521
323
161
111
380
187
592
430
120
135
146
182
214

95
762
612
171
149
170
485
292
266
230
191
364
120
308
272

92
100
215

70
540
299
278
227

72
318
130
225
167
272
213
270
290
230

77
270

93
338

H

12
-12
~12
'12

12
‘12

13
’13

13
'13

13
'13

13
'13

13
-13

13
-13
-14

14
~14
-14

14
-14

14
-14

14
-14
'14
~14
-15

15
-15

15
-15
-15
-15
'15
-15
-16

16
-16

16
~16
-l6
-16
-17
~17
-17
-17

K

mum—INJ‘bN—‘OOIOmbUNNHF‘NO‘mbbUUNNI-‘OOOO‘0".”U'I'JUN'Vl—HOQO‘O‘UTbu

F085 FCAL
189 199
270 274
204 227
124 137
182 187
277 289
105 99
351 337
290 274
313 331
229 241
151 158
110 97
304 297
248 224
113 123
111 151
310 296
215 243
342 330
119 109
101 82

74 93
193 183
105 93
270 252
202 198

79 84
192 193
295 285
329 361
298 321
265 306
156 175
160 171

98 105
379 376
132 148
200 217
428 427
287 348
134 143
107 126
266 262
175 188
201 200
365 366
167 185
110 110
351 349

H

'17
'18
'18
'18
'19
'19
‘19
-20
'20
-21
-21

I 8
o<:c>3:5c>o 8

I I I I I I I I I I I I
NNNNNNNNNNNNt—H—o—I—t—v—rut—www.—1—r-I1—ov—Io

K

83—-b<531u-3~bc>o

1"

H1—
O‘O‘U'IU'IJ-‘bwUNN—‘HOOCDCDN‘JJ‘O‘mmbbuUNHHOQO‘Lflbwm-l

FOBS FCAL
138 151
447 437
309 333

81 93
197 190
142 172
130 149
197 210
159 152
120 142
83 103

= 9 *6

39 16
429 483
227 191
474 510
427 442
254 206
104 99
297 316
178 179
59 92
130 131

1126 1068
1054 1021
519 561
168 238

81 100
48 39
259 248
231 202
148 185
235 252
192 223
195 175
306 380
303 359

64 70
134 164
504 549
773 780
222 261
175 171
265 259
414 414
403 437
351 350
300 265
186 225

APPENDIX B (Cont'd)

H K F085 FCAL

-2 8 121
2 8 132
-2 9 317
2 9 296
2 10 78
-3 1 106
3 1 363
-3 2 120
3 2 146
-3 3 972
3 3 818
-3 4 404
3 4 66
-3 5 83
-3 6 242
3 6 189
-3 7 142
3 7 263
-3 8 191
3 8 169
-3 10 290
-4 1 320
4 1 133
-4 2 1015
4 2 933
-4 3 85
4 3 251
-4 4 207
4 4 287
-4 5 311
4 5 183
-4 6 173
4 6 195
-4 8 165
4 8 171
-4 9 287
4 9 206
-5 1 560
5 1 843
—5 2 109
-5 3 720
5 3 S45
-5 4 251
5 4 159
5 5 153
-5 6 226
5 6 186
-5 7 173
5 7 207
-5 8 166
5 8 213

awiii

114
135
318
287

64

74
370
150
168
922
760
397

83
122
240
205
169
276
198
144
320
288
108
961
920
193
246
240
303
324
176
175
197
177
196
249
209
593
826
121
776
546
262
178
159
227
235
201
207
202
211

#9011114NNHF‘OQO‘O‘UIWD‘L‘UWNNF‘WOWNWUI“puwNNF-‘HOO‘IO‘O‘UIUIkaUNnH-‘H

F085

146
409
322
745
672
237
269
291
144
400
247
184
225

70
255
198
514
366
103

84
588
291
402
334
159
169

81
196
153
461
353
507
249
302
163
356
160
313
274
403
241

90
271
474
226
109
156
470
315
468
515

FCAL

137
426
325
726
630
201
247
263
156
438
226
192
247

78
216
236
550
326
158
120
559
336
329
375
192
169

86
176
142
406
362
550
262
358
188
367
144
320
246
348
272
143
273
504
199
177
169
494
297
526
474

H

-9
9
-9
-9
10
-1o
10
10
-1o
10
~10
10
-10
10
~10
«-11
11
11
-11
11
-11
11
-11
11
-11
-12
12
~12
12
12
-12
12
-12
12
-12
-13
13
-13
13
--13
13
-13
-13
--13
14
-14
14
~14
14
14

K

¢wuNNH3N0&¢UUHH~OO‘O‘UIU1$‘UUNNWO‘O‘&#UUNHF‘OO‘O‘WU'I'L‘6‘UNNWOO‘UTUW

F085

121
195

87
119
136
408
315
113
279

87
506
323
216
216
280
298
200

85
387
273
543
341
175
142
222
513
451
126
112
182
381
155
203
145
203
253
297
377
288
273

92
122
257
223

74
438
360

80
107
158

FCAL

158
199

54
119
162
365
314
116
299

97
509
343
171
216
262
318
222

95
418
261
554
320
174
151
194
518
446
114
120
180
373
199
222
175
199
224
289
352
317
216

95
145
276
219

99
415
376

90
112
168

APPENDIX B (Cont'd)

H K F085 FCAL

-14
-14
-15

15
-15
~15
-15
--15
--15
-16
~16
-16
-16
-17
~17
-17
-18
~18
-18
-18
-19
-19
-19
-2o
-20
-21

8
t

HHHHhfiHI—It—IHHHHOOOOOOOOO

mgn¢~kcauamrunvnwac>m-qow838wruuua r

1—ambuwombmow~a~¢-m~o~bw-mo

293

97
227
172
112
115
118
281
173

82
270
128
218
234
220
103
213
204
162

86
149
303
105
234
103
142

10

530
100

64
254
523
143
140
232

56
188
326

80
257
184
248
158
293
307

83
500
511

xix

324

91
246
179

88
159
140
305
187

91
306
122
229
265
243

92
258
236
155
103
160
322
123
241
125
159

8'8

492
143

50
263
648
149
142
247

62
193
301

88
301
170
.306
135
307
325

70
488
497

H

K

omflflo3m¢¢hflw--coommoa~m m8cuu--~o~1woa~mbcuummoommoo‘

F085 FCAL
261 235
165 185
236 236
246 260
149 171
184 198
226 191
196 220
568 605
126 140
326 400
703 675

98 79
189 208
146 158
323 359
244 256

88 92
173 242
454 468
363 302
238 261
413 449
379 382
307 304

65 57
367 354
472 483
237 241
229 256
237 234
211 200
113 126
326 334
421 436
331 373

96 105
211 237
141 181
384 351
169 154
400 424
625 610

86 79
156 184
227 240
267 273
298 289

97 98
581 554

H

5
-5
5

K

m4~bwwm~aommammbbduwrvu—oqqaombbwwm—n—camrwommbuwmm-o

FOHS FCAL
72 89
870 820
390 389
175 160
364 363
334 307
305 350
196 170
294 300
415 399
203 178
220 203
218 204
131 96
1411 1381
671 667
138 151
270 273
233 216
281 321
248 259
416 418
541 527
218 220
134 112
294 279
170 176
229 234
78 68
869 784
410 393
136 134
454 463
129 86
159 184
117 133
120 119
532 533
487 459
288 274
188 194
169 164
818 792
813 761
196 190
223 227
246 279
367 352
489 505
462 429
220 233

APPENDIX B (Cont'd)

H

K

bwwmxh-oaoxqiommbbump—~04;ambbuumwuooomoommbwa—~Gama-J1

FOBS'FCAL
69 77
135 88
172 190
244 238
137 103
408 401
346 358
281 304
229 210
168 150
82 95
624 630
288 308
164 149
138 158
125 116
96 79
589 682
344 391
69 88
122 122
109 116
177 740
326 328
377 406
119 150
91 107
192 207
140 138
123 109
71 96
400 415
295 298
193 219
216 244
355 375
147 154
167 125
209 212
237 271
150 166
141 146
246 212
591 596
289 252
81 134
118 117
130 145
116 78
215 228
172

163

XX

H

-12
-12
-l3
l3
-13
13
13
’13
‘13
-13
~14
l4
-l4
14
~14
l4
-l4
-l4
-l4
-14
'14
'15
‘15
'15
-15
'15
-l6
-l6
-l6
-16
-16
-17
'17
-I7
-17
'17
'18
-18
~19
-l9
'19
'20
-20
-21

*4}

COCO

K

whomuv-aoomum—uobwcombmt—wombummv—u—comomwNNF-‘HNO‘

l—

éUNH

FORS FCAL
210 224
439 460
350 365
244 258
190 224
155 176

68 84
I31 114
251 287
319 330
335 336
224 225

78 79

71 83
I79 225

77 102
185 197

90 63
107 124
214 216
453 490
267 262
297 327
109 149
273 263
I92 166
450 478
153 157
250 262
116 133
240 264
325 319
128 123
152 147
208 I96
180 171
424 445
277 306
218 223
112 86
126 133
280 307
131 167
177 189

:11 .4}

83 78
526 557
84 98
390 385

H

I I I
IVIV nJh)NJ—'~'~'--—'-—-‘~'—'—'c>c>c>c>

I I I I I I I I I
UNNNNNNNNN

UUUUUUWUUUUU

II II I
¢9¢99k¢

K

O‘LflbJ-‘UNNQQNIOO'L‘9UUNN~H~O~O®mGJU1LnJ>¢wNNHQCDNJ‘O‘J-‘I‘UJUNHHOQO‘W

FOBS FCAL
429 376
101 144
118 96
266 306
382 390
226 214

74 48
496 534
904 523
382 378
125 128
138 127
130 156
200 228
186 183
161 138

88 104
S60 543
526 516
245 223
292 287
359 377
446 437
133 95

93 92
269 261
101 89
176 205
240 260
207 223
169 112
382 414
90 125
123 172
S46 539
496 515
672 643
S6 107
147 174
155 157
271 310
171 147
176 172
731 743
626 586
286 305
140 150
116 112
416 406
152 189

APPENDIX B (Cont'd)

H

a
4
-4
-s
5
-5
5
-5
5
-5
5
5
-5
5
6
-6
6
6
-6
6
-6
6
-6
6
-6
-7
7
-7
7
-7
7
7
-7
7
7
-7
8
-8
8
-8
8
-8
8
-8
8
-8
8
-8
-9
9

K

~‘~'02h3\mgflknbLduHVPu—am'dO‘O£n$‘¢WJLJ-H~O3‘3LflLflt‘ktdfiderabm-dc‘$Ln¢‘uLJ—vwwo333

248

xxi

FOBS FCAL
267 P64
135 149
192 190
598 670
441 392
514 527
401 430
590 620
138 144
200 279
108 122
226 242
221 212
193 172
325 345
920 839
246 251
221 227
100 126
124 147
489 480
121 12%

92 47
160 214
170 153
622 615
215 200
420 372
322 319
339 344
347 321
104 105
233 268

86 124
129 139
135 96
203 201
752 735
150 167
126 114
274 271
242 244
141 153
511 513
168 187
127 115
185 180
187 185
246 281

259

H

-10

-12

-13

13
-13
~13
-13
~13
-13
-14
-14
-14
-15
-15
~15

ou~o~mmm~1omu-mo~ms~ummm~1mbbuwmwwomommbbuummoammbauwm

FOIS FCAL
120 128
563 584
190 153
362 380
339 333
118 16h

97 92
103 94
119 123
462 446
347 321

91 121

87 89
335 333

72 87
408 406
209 228
105 84
138 123
226 220
311 319
247 263

97 172
390 368
239 263
254 225
195 217

94 147
108 130
165 165
288 298
356 401

93 87
146 157
103 116
173 185
158 169
207 186
220 239
190 169

88 97

96 125
282 318
199 212
220 239

90 179
268 282
116 116
203 231
163 182

H K

-15
~16
-16
~16
-l7
-17
-17
~17
-18
-18
-18
-19
~19
-19
~20
-21

a
a

F-‘F-‘I-‘O-‘I-‘OOOOOOOO

II I
---

I I
pin—twp

-¢w~ms~mo~t~w~o~mm~1

r

t‘©UNNHOOQQO‘OLflml-‘UwNN—‘HOO‘IO‘UII‘UNHO

12

368
57
53

146

437
93

113

208
92

130

322

450
94

267

123

134

215

403

427

120
87

191

193

393
619

70

97
190
270
263
320

F085 FCAL
217 260
238 228
128 129
115 117
212 246
204 211

83 68
131 160
248 260
102 126
171 183
190 227
193 189

96 106
195 192
179 207

{’4}

315
42
53

140

434
77
98

158

157

171

328

464
96

286
96

158

1954

407
427
137
146
183
204
390
665
101
100
212
275
255
328

APPENDIX B (Cont'd)

H

K

--o<:anmo~mancnbuJurumw—nvocas1qcranbs~unu—-<>c>man0‘9xflULbUJUFURH"*'°CD‘V*O‘0

xxii

FOBS'FCAL
122 146
177 200
286 264
330 309
109 105
123 165
430 418
527 483

84 74
160 188

87 106
238 242
325 343
194 149
327 303
292 266
191 183
271 276
154 168
304 364
615 565
225 250
281 306
278 280
323 314
146 124
366 364
141 179
226 252
363 369
332 337
127 134

77 82
446 457
291 278
217 225
337 327
261 280
338 326
178 178
126 130
121 95
310 289
288 258
193 190
200 180
551 539
429 382
136 98
183 151

H

K

uwNOOQOWWUUNNHHmOW¢bUNNF‘GO0&03‘fl‘flJ-‘QJJNNF‘F‘OQQT’J‘flbl-‘LAUJN

F085 FCAL

74 93
181 207
271 283
281 258
481 454
156 168
133 139
191 189
246 261
263 261
126 173
510 519
261 277
124 161
299 307
257 263
128 132
69 70
281 251
293 309
218 213
171 175
98 75
106 146
635 702
394 430
153 163
140 148

87 86
267 264
410 414
244 268
220 229
131 126
109 113
S47 560
282 278

88 121
133 174
122 131

93 130
399 368
182 225
195 209

91 82
689 676
311 335
200 210
100 129
229 261

 

H

-10

10
'10
-10
~11

11

ll
'11

ll
-11
'11
-11
-ll
’11
-12

12
'12
-12
'12
‘12
‘12
‘13
'13
“13
‘13
'13
-13
'14
-14
'14
-14
-15
-15
-15
~16
'16
'16
-16
-16
~17
'17
'17
'18
‘18
-19
-20

{-8
U
0

K

owbomu—mbwmo3m-ta~moqa~mbwwqomt~uoaw~3mtuum-umbb

Mt“!—

FOBS FCAL
497 494
177 208

97 133
103 55
359 319
247 239
114 135
129 144
122 130
160 169
273 292
228 237
151 187
168 154
487 441
266 283

98 91
170 127

98 137
215 251
396 394
275 299

92 116

85 95

9O 60
325 333
109 119
316 377
122 150
157 158
421 473
254 243

79 55
241 236
326 313

99 117

87 110
167 170

87 103
202 210
136 143
118 140
344 362
165 175
232 262
363 384

= 1‘3 4H!-

66 105
564 522

APPENDIX B (Cont'd)

H

wwwaNNNNNNNNN—‘HH—F‘HH-iF‘HI-‘I-‘COOOD

I II
WUUQU

II I I I I II
fiflwbbt‘l‘bbt‘bt‘bu

K

UWHU‘O‘LflWkUNNF‘I-‘m\INO‘O‘J-‘UUNHF‘GDO‘UWUWJ‘PUNMWNNG‘U‘DrI-‘IJUNt-‘HDO‘W9U

F085 FCAL
72 50
249 238
257 282
126 154
81 79
290 300
408 439
52 43
387 351
408 407
278 247
143 154
121 98
169 180
118 80
110 119
67 86
568 525
529 492
111 102
182 191
226 258
355 356
136 147
142 149
117 143
336 372
433 428
98 86
299 247
328 352
322 330
165 167
187 174
172 149
200 236
174 187
109 113
193 193
533 510
355 366
216 210
113 120
331 349
100 55
90 121
187 219
424 438
350 309
274 252

xxitl

H

-10

10
-10
-10
-10
-11

K

Hambmmfia‘k-PUUHHCDU‘UW9UNNF'QNO‘O‘UT9PUUF‘I—O‘O‘U14PJ-‘UUNNH'—mNNO‘O‘L‘

F085 FCAL
427 420
191 198

83 78
144 123
200 217
169 154

86 102
207 180
604 546
204 202
178 179
169 148
105 117

73 79
324 278
104 113
218 200
475 438
125 130
350 340
182 156
363 403
110 106

98 105
258 268
103 100

97 78
145 130
243 254
448 418
262 238
101 9?
170 165
446 434
155 180
145 156
276 314
182 186
375 376
134 140
241 220
103 144
185 165
119 109
317 337
246 264
168 161
264 266
151 156
217 208

'_ ‘-

,1.v ‘- __

cy,‘ A' 2
3.

i1 !

 

APPENDIX B (Cont'd)

H K F085 FCAL H K FOBS'FCAL H K F095 FCAL
11 1 172 200 2 1 202 230 6 3 150 132
-11 3 328 310 -2 2 160 181 -6 4 150 120
~11 5 127 148 1-2 3 293 272 6 4 142 157
-11 6 83 82 2 3 124 99 -6 5 ‘ 97 98
-ll 7 166 160 1-2 4 194 199 -6 7 291 310
-12 2 297 291 2 4 187 165 -7 o 85 78
-12 4 92 102 -2 6 155 152 -7 1 307 282
-12 6 92 105» 2 6 150. 145 7 1 265 255
-l3 l 185 205 .-2 7 212 195 -7 2 144 155
-13 3 192 181 2 7 219 232 7 2 106 118
-13 6 145 166 -3 o 190 204 —7 3 269 277
~13 7 184 221 3 o 206 212 7 3 86 106
—l4 2 312 342 -3 1 506 473 -7 5 124 81
~14 9 111 108 3 1 262 251 —7 6 195 215
-14 6 89 96 -3 2 229 234 -8 o 638 562
-15 1 138 121 3 2 109 114 3 0 P64 268
-15 3 262 272 3 3 269 227 a 3 102 122
~15 4 131 144' -3 4 224 239 -8 4 428 396
-15 6 119 147 1-3 5 148 155 8 4 133 161
-16 2 250 234 3 5 203 206 -8 5 114 115
-16 3 91 82 -3 6 216 183 -8 7 183 189
-16 5 151 134 3 6 130 127 -9 o 91 63
~17 l 142 131 -3 7 111 121 -9 1 385 363
-l7 3 170 168 -3 8 183 199 9 1 228 234
-17 4 135 145 .4, O 620 628 -9 2 159 173
-18 2 204 212 4 o 262 246 -9 3 201 228
-19 1 197 211 4 1 257 240 -9 5 213 176
46 L = 14 #§ -4 3 299 295 -9 6 185 195
4 4 210 179 -10 o 544 534
0 o 587 630 -4 6 174 164 -10 2 138 152
o 2 231 252 4 6 171 173 -10 4 465 433
0 3 68 81 -4 7 336 356 '10 5 150 159
0 4 226 223 -5 0 120 169 '10 7 132 129
0 5 101 113 -5 1 361 352 -11 o 121 152

0 6 107 88 5 l 213 212 ~11 1 244 271
0 7 198 157 -5 2 89 80 '11 5 269 268
-1 0 98 104 5 2 254 243 '11 6 191 202
-1 1 514 547 -5 3 138 175 '12 0 142 157
1 1 458 446 s 3 197 139 -12 2 121 134
-1 2 182 176 -5 4 101 119 -12 4 248 238
1 3 55 56 5 5 239 242 ~12 6 122 115
-1 4 95 90 -S 6 280 274 -l? 7 181 70%
—1 5 343 233 S 6 143 149 -13 l 190 193
1 5 .93 204 -5 8 165 160 -13 3 119 135
-1 6 202 185 -6 o 438 373 ~13 5 114 101
1 6 223 214 6 o 182 197 -13 6 198 188
-2 o 624 650 -6 1 97 146 -14 o 203 196
2 o 647 671 6 2 113 105 -14 6 85 98
-2 1 195 148 -6 3 139 140 -15 1 241 250

xxh:

 

 

H

~16
‘17
‘18
‘18
‘18
‘19
‘19

t
t

I I I I I I I I I I
QUwVNNNNNNNNN--~——30000

J'lJIJ-‘8bbbJ-‘k4‘wgddulul

K

“OUFOI‘Q

-J1Jlbuumm~qa~¢buuwumammbb-uummabbuu—~ambum I'-

FOBS FCAL
251 251
195 226
288 311

90 124
84 102
103 128
206 240

z: 15 III!

289 252

87 112
100 82
178 186
130 120
347 340
416 408
178 170
223 230
123 124
100 122
130 134
291 266
371 385
103 121
58 77
96 84
117 133
148 131
214 201
172 148
78 79
456 436
213 213
133 131
288 276
154 139
139 100
130 126
138 144
70 104
376 376
138 353
201 212
121 109
152 133
197 203
114 146
333 301
101 136

APPENDIX B (Cont'd)

H

-5
5
-5
5
-5
-5
-6
-6
6
-6
6
-6
-6
-7
7
-7
7
-7
-7
-7
-8
-8
-8
-8
-9
-9
-9
-9
-9
~10
-10
-11
-11
-11
-11
-12
-12
-12
-13
~13
-13
-14
-14
-14
-15
—15
-15
-16
-17
-17

K

UflmbwflmbNO‘U-‘mbma‘w\IF‘U'INNO‘bU—‘UIkNF"13‘kww-‘h‘J'IbUUNN-‘NO‘4‘50U

F085 FCAL
187 165
208 194
267 213

96 88
191 204
124 138
177 190
353 371
296 277
225 238

68 63
158 141
237 231
156 130
175 152
339 351
104 111
375 344
166 167
102 101
163 148
223 193
183 148
285 267
200 238
309 277
185 149
129 157
126 135
271 246
186 178
183 209
104 115
267 261
109 107
343 305
117 146
124 116
179 197
253 254
107 122
354 367

99 101
182 178
182 175
162 168
121 103
224 237
100 69

98

97.

XXV

H

‘18

III!

I
NNNN'UNh‘I-‘HH—I-‘HF'OOOOO

I
MN

II
(JUN

-3

K

N

combat-numb6‘91)UNflOOOWUNNflWOOO‘PbUUNHOO3"J1msz-‘U-‘Ome-‘O f’

FOIS FCAL
119 130
= 16 II.

904 883
181 163
121 124
153 143
60 55
391 379
550 529
396 393
116 87
101 110
162 175
130 135
159 160
814 789
414 407
194 187
170 174
177 135
102 90
154 150
157 149
97 104
199 248
170 169
317 292
193 200
238 214
88 98
84 76
229 204
134 128
389 363
118 121
127 149
83 92
227 225
101 90
112 113

72 63
140 136
169 162
158 157
144 174
136 96
165 166
235 193

 

H

6
-6
-6
-6
-7
-7
-7
-7
-7
-8
-8
-8
-9
-9
-9
-9

-10

--10

-10

-11

-11

-11

~12

-12

-12

--13

-13

-13

-14

-14

~15

-15

-16

~16

-17

99

0
0
l
l
1
l
1
2

2
‘2
-2
-3

K

H2308"OOWN~¢NOWUHO¢OOU1U~UIéOO‘UN—‘D3‘3?th

“WUNN‘FUNH'I'JPN I.

F085 FCAL
164 167
134 116
113 95
101 84
107 118
247 246
108 100
221 198
209 226
318 312
202 170

94 118
223 222
164 125
127 135
196 179
305 319
225 216
103 95
204 208

97 87
158 176
195 221

94 107
173 190
189 161

78 92
107 114
187 130

85 119
146 183

75 107
163 146

80 81
156 186

:17 {HI

135 135

58 73
330 334
197 205

86 97

96 111
128 105
180 169
213 224
122 114
101 103
333 303

APPENDIX B (Cont'd)

H

3
-3
-3
-3
-4
-4
-4
-4
-5
-5
-5
-6
-6
-7
-7
-8
-8
-9
-9
-9

-10

--10

-11

-—11

-12

-12

-13

~13

-13

~14

--15

GO

t—t—u—u—oa

-3
-3
-4
-4
-5

-6
-6
-7

K

“N900HbNUHWN‘PUHU’NémeL‘U-‘JI¢UN&UN“

<ac-oru—-b<:—-=<383~t—c>—ua P

FOBS'FCAL
111 116
120 144
200 202
112 107
290 288
143 139
101 88
126 128
164 164
222 199

99 108
303 329
182 174
209 157
105 89
238 200
127 120
103 102
173 137

85 96
228 185
107 108
129 123
202 210
250 258
114 122
141 156
247 260
119 114
253 254
142 167

= 18 III!»
510 540
108 89
194 222
298 299
257 282

74 70
492 519
213 255
210 225
181 217
145 137
131 128
93 86
108 92
91 95
91 107

xxvi

H

-7
-7
—8
-8
-9
‘10
~11
-12
~13
-14

fl.

-3
-4
-6
-7
-8

K

cpcch—Iu—‘ONI"

r

N-‘NNI"

F085 FCAL
130 166
103 92
154 105
100 96
103 102
200 190
176 135
214 192
129 109
145 125

z: 19 .8
122 117
195 184
204 200
116 103
185 181

 

 

APPENDIX C

Interior Angles of the Planes Comprising the D

Square Antiprismatic Polyhedron of Nb(DPM)4

4

2.:.§4- .-

'6 (5"

 

APPENDIX C

Interior Angles of the Planes Comprising the D4

Square Antiprismatic Polyhedron of Nb(DPM)4

 

Molecule A Molecule B
Oxygen Atom Angle, Angle,
Numbers deg. deg.
04—01-02 88.8 90.7
01-02-03 88.5 89.6
02-03—04 91.4 90.3
03—04-01 91.1 89.4
08-05-06 91.7 93.0
05-06-07 87.6 88.4
06-07-08 91.4 91.9
07-08-05 88.8 86.6
08-01-05 55.2 56.0
01-05-08 61.3 61.3
05-08-01 63.5 62.7
05-01-02 61.4 61.3
01-02-05 65.4 62.7
02-05-01 53.2 56.0
05-02-06 58.7 54.5
02-06—05 59.8 60.1
06-05—02 61.5 65.3
03-02-06 60.8 60.7
02—06-03 55.4 55.1
06-03-02 63.9 64.2
07-03-06 56.5 54.9
03-06-07 64.6 62.9
06-07-03 58.8 62.3
04-03-07 62.3 61.8
03-07-04 50.3 55.7
07-04-03 67.4 62.6
07—04—08 59.2 55.6
04-08-07 61.2 60.2
08-07-04 59.6 64.2
08-04-01 63.8 59.6
04-01-08 60.6 65.1
01-08-04 55.5 55.2

 

'1