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L‘HRARY
itmhigan State
university

 

 

“—con 0

 

This is to certify that the

thesis entitled

Syntheses, Structures, and Magnetic Properties of
Lanthanide Complexes of 2,2',2"-Nitn'lotriphenolates

presented by

Lars Peereboom

has been accepted towards fulfillment
of the requirements for

MS. degree in Chemistry

 

O.“ (as;
/ Major prokéor

Date $9) August Zwl

0-7639 MS U is an Affirmative Action/Equal Opportunity Institution

 

 

 

 

PLACE IN RETURN BOX to remove this checkout from your record.
TO AVOID FINES return on or before date due.
MAY BE RECALLED with earlier due date if requested.

 

DATE DUE

DATE DUE

DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

6101 C'JCIRC/DatomeS-nfi

 

 

SYNTHESES, STRUCTURES, AND MAGNETIC PROPERTIES OF
LANTHANIDE COMPLEXES OF 2,2’,2"-NITRILOTRIPHENOLATES
By

Lars Peereboom

A THESIS
Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree

MASTER OF SCIENCE

Department of Chemistry

2001

ABSTRACT
SYNTHESES, STRUCTURES, AND MAGNETIC PROPERTIES OF
LANTHANIDE COMPLEXES OF 2,2',2"-NITRILOTRIPHENOLATES
BY

Lars Peereboom

Tripod ligand 2,2’,2”-nitrilotriphenol (triol) can readily be deprotonated to
form a trianionic ligand which reacts with lanthanide (Ln) chlorides; variation of .
this reaction’s stoichiometry allows assembly of 1:1 and 2:1 ligand2lanthanide
complexes. X-ray crystallography finds that La and Gd 1:1 complexes form
phenoxide bridged dimers with Ln-Ln distances of 3.9745(3) and 3.8719(8),
respectively. Gd and Yb 2:1 compounds formvtrianionic “sandwich” cores with
two ligands capping the lanthanide; bridging sodium ions then link these
complexes into parallel chains. Magnetic studies show the Gd 1:1 complex to
have antiferromagnetic Gd-Gd coupling (J = -0.058, assuming g=2.0) in the
normal range for systems with similar Gd-Gd distances. Three related ligands,
tris(2—hydroxy-5-nitrophenyl)amine, tris(5-bromo-2-hydroxyphenyl)amine, and
tris(4,5-dibromo-2-hydroxyphenyl)-amine were synthesized, and the trinitro

compound’s coordination chemistry with LaCla explored.

To Lisa for putting up with me.

LIST OF FIGURES............................ vii
INTRODUCTION ............................................................................................ 1
1.1. CONCEPTUAL OVERVIEW ......................................................................... 1
1.2. LITERATURE REVIEW ............................................................................... 2
1.3. PHENOXIDE COMPLEXES OF LANTHANIDES ............................................... 5
RESULTS & DISCUSSION ......................................................................... 9
2.1. SYNTHESIS OF LIGANDS ........................................................................... 9
2.2. SYNTHESIS OF COMPLEXES ................................................................... 12
2.3. NMR ANALYSIS .................................................................................... 13
2.4. MASS SPECTROMETRIC ANALYSIS .......................................................... 17
2.5. X-RAY STRUCTURES ............................................................................. 18
2.6. MAGNETIC STUDIES ............................................................................... 26
EXPERIMENTAL ......................................................................................... 31
3.1. EQUIPMENT AND CHEMICALS USED ......................................................... 31
3.2. SYNTHESIS: ...................................................................... ; ................... 32
3.2.1. Ligands ........................................................................................ 32
3.2.2. Complexes ................................................................................... 37
3.3. IR ........................................................................................................ 39
3.4. NMR STUDIES ...................................................................................... 39
3.5. SQUID MEASUREMENTS ....................................................................... 40
3.6. X-RAY CRYSTALLOGRAPHY .................................................................... 41
APPENDIX ..................................................................................................... 44
LIST OF REFERENCES ............................................................................. 74

TABLE OF CONTENTS

LIST OF TABLES

Table
2.1 Bonds and angles of lanthanide triolate complexes... .. 1 8
2.2 Magnetic coupling constants for gadolinium dimer complexes. 29
A1 Crystallographic data for La2(triolate)2-BDMSO 28... 53
A2 Crystallographic data for Gd2(triolate)2-4DMSO 29... 54
A3 Crystallographic data for NaaGd(triolate)2-2H20-60H30H 32 55
A4 Crystallographic data for NaaYb(triolate)2-2HZO-5CHaOH 33... 56
A5 Atomic coordinates 8x 10‘), equivalent isotropic displacement
parameters (A2 x 10 ), and occupancies for
La2(triolate)2-GDMSO 28 57
A6 Anisotropic displacement parameters (A2 x 103) for
Laz(triolate)2-6DMSO 28 61
A7 Atomic coordinates 3x 10"), equivalent isotropic displacement
parameters (A2 x 10 ), and occupancies for
Gd2(triolate)2-4DMSO 29 63
A8 Anisotropic displacement parameters (A2 x 103) for
Gd2(triolate)2-4DMSO 29 65
A9 Atomic coordinates 3x 10"), equivalent isotropic displacement
parameters (A2 x 10 ), and occupancies for
NaaGd(triolate)2-2H20-60H30H32.................................... 66
A. 1 0 Anisotropic displacement parameters (A2 x 103) for
NaaGd(triolate)2-2H20-SCH30H32.................................... 68

A.11 Atomic coordinates 3x 10‘), equivalent isotropic displacement
parameters (A2 x 10 ), and occupancies for

NaaYb(triolate)2-2H20-5CH30H 33... 69
A. 1 2 Anisotropic displacement parameters (A2 x 103) for
NaaYb(trio|ate)2-2HzO-5CH3OH 33... 72

Vi

TABLES OF FIGURES

Figure
1.1 General cage structures of atranes and aratranes. Naming

follows the simple form of naming X followed by “atrane” or

”aratrane” (i.e. Xatrane). Thus when X=B, the structures would

be boratrane and boraratrane... 2
1.2 Known compounds derived from tris(2-hydroxyphenyl) amine... 3
1.3 Aluminum triolate dimer 6a, showing the phenoxides bridging

the two aluminum ions... 4
2.1 1H- NMR spectra of Naatriolate 27 mNa3La(triolate)2 31 and

Na3Yb(triolate)2 33 In 020.. 15
2.2 1H-NMR spectra of Nagtriolate 27 titrated with LaCla in 020.... 16
2.3 ORTEP drawings of (LaTriolate)2-6DMSO 28 and

(GdTriolate)2-4DMSO 29... 20
2.4 Core structure of NaaGd(trioIate)2-2H20-6CH3OH 32 clearly

Showing the diaratrane cage... .. 22
2.5 View perpendicular to the metal-containing planes of

NaaGd(triolate)2-2H20°SCH30H 32 and

NaaYb(triolate)2-2H2Om SCH30H 33; carbon and hydrogen atoms

omitted for clarity... ..24
2.6 End on view of NaaGd(trioIate)2-2HzO-GCHaoH 32 and

NaaYb(triolate)2-2H20-SCH30H 33; carbon and hydrogen atoms

omitted for clarIty 25
2.7 xT vs T curves for (o)Gd2(triolate)2-4DMSO 29;

(D)NaaGd(triolate)2-2H20-60H30H 32;

(+)Yb2(triolate)2-4DMSO 30;

(x) Na3Yb(triolate)2-2H20-SCH30H 33;

(-) calculated fit for Gd 1:1 29.... 27
AI FTIR spectrum of “Yb2(triolate)2-4DMSO complex 30

(KBr pellet). .. . . 45

vii

A2

A3

A4

A5

A6

A7

A.8

FTIR Spectrum” of NaaGd(trIolate)z-2H20-60H30H 32

(KBr pellet)... . . 46
FTIR spectrum of HNaaLa(triolate)2-2H2O-6CH30H 31

(KBrpellet)... 47
FTIR spectrum of Na3(triolate) 27 (KBr pellet)... 48

Drawing of La2(triolate)2-SDMSO 28 showing thermal ellipsoids
and atom labeling scheme. Hydrogens are omitted ................. 49

Drawing of Gd2(triolate)2-4DMSO 29 Showing thermal ellipsoids
and atom labeling scheme. Hydrogens are omitted .................. 50

Drawing of NaaGd(trioIate)2-2H20-GCH30H 32 showing
thermal ellipsoids and atom labeling scheme.
Hydrogens are omitted... 51

Drawing of NaaYb(triolate)2-2H20-5CH30H 33 showing thermal
ellipsoids and atom labeling scheme.
Hydrogens are omitted... 52

viii

INTRODUCTION

1.1. Conceptual Overview

Recent work from the research labs of Dr. J. E. Jackson has focused on
ionophoric triaryl X systems 1 where X may be a radical center, carbocation,
amine, or borane‘. It was found that these "tripod ether" complexants can be
assembled into magnetically interacting complexes using metal ions.2 Besides X-
ray structural characterization of the free triaryl X compounds, their ion binding
behavior has been investigated using pulsed EPR, NMR, and UV-ViS
techniques.3 Inverting the theme of magnetism based on ligand—centered
radicals, my research has focused on the structurally related compounds 2
below in which paramagnetic metals are complexed by diamagnetic ligands. It is
the synthesis of these compounds and their structural, spectroscopic, and

magnetic characterization that form the body of this thesis.

 

 

 

H30\ "M

0 o
-x
3

O

Hac’ / M = La, Tb, Gd, Yb

3
1 2

Lanthanides are oxophilic and generally behave as hard ions with no
orbital constraints on their bonding. Their complexation is therefore similar to
that found with alkali metals,‘ the principal Class of ions whose coordination has

been explored in this structural framework. The Lanthanides’ unpaired electrons

are in f orbitals which are buried inside the filled s and p orbitals. This shielding
prevents the f electrons from participating in directional bonding interactions.
The bonds of lanthanides can thus be viewed as Simple electrostatic interactions

between their stable 3+ ions and the ligand.

1.2. Literature Review

(a) Atranes & related systems

 

 

I m—x x
t, ..
l l3 a

atrane aratrane

Figure 1.1: General cage structures of atranes and aratranes. Naming follows
the simple form of naming X followed by “atrane” or “aratrane” (i.e. Xatrane).
Thus when X=B, the structures would be boratrane and boraratrane.

In 1966 Frye et al. first reported the synthesis of 2,2',2”-nitrilotriphenol 3.5"5
This ligand was prepared via the Ullmann condensation of ortho-anisidine and 2-
iodoanisole followed by cleavage of the methyl ethers. Frye also used it to make
pentacoordinated silicon derivatives. For example, the ligand readily reacts with

phenyltriacetoxysilane to form the phenylnitrilotriphenoxysilane 4 as shown in

Scheme 1.1.
Scheme 1.1,
i
”0 0 Si
ZSi(OAc)3 + __.CC|4 i
N N
3 3
3 4

Miller and BUrgi made a series of systems similar to Frye's, but
incorporating boron, aluminum, and phosphorus. In X-ray diffraction studies, the
free boratrane 5a Showed a bond between the boron and the central nitrogen.7
In later work the same authors reported X-ray structures of the boron triolate
pyridine and quinuclidine adducts 5b and 5C.” The latter compounds showed
long intracage B-N distances, confirming that adduct formation destroyed the
intramolecular B-N bond. Shortly thereafter, compounds 5a, 6a, and 7a were
also reported by Paz-Sandoval et al., characterized only by NMR and elemental

analysis.9

2
4 M=Si, Z=phenyl
5a M=B; 5b M=B, Z=pyridine; 5c M=B, Z=quinuclidine

O M
I 6a M=AI; 6b M=Al, Z=pyridine; 6c M=Al, Z=quinuclidine
N

7a M=P; 7b M=P, Z=H, charge +1; 7c M=P, Z=O
8 M=Ge, Z=O
3 9 M=Sn, Z=phenyl

Figure 1.2: Known compounds derived from tris(2-hydroxyphenyl) amine.

The aluminum complex that MUIIer prepared requires an extra
coordinating atom on the open faces to give 5-Coordinate aluminum. Unlike the
boron triolate, the aluminum triolate 6a formed a dimer with two phenoxy
oxygens bridging two aluminum centers as shown in Figure 1.3.10 The pyridine
and quinuclidine adducts 6b and So were monomeric and structurally similar to

those found in the boron series.

O
-----2

 

O

N

Figure 1.3: Aluminum triolate dimer 6a, showing the phenoxide bridging the two
aluminum ions.

The X-ray structure of the neutral phosphatrane 7a showed no evidence
for interaction between the P and the N. One unique chemical feature, however,
is that this compound gets protonated on P, not the more electronegative N. This
unusual Site preference is apparently due to a strong N-P interaction in the
protonated system. No structural data were given to confirm this N-P
interaction,11 but the analogous behavior has been thoroughly characterized in
the parent aliphatic phosphatrane.12

Livant et al. reacted triol with germanium tetraethoxide resulting in oxygen
bridged dimer 8“. This dimer consist of two germa-aratranes bridged by a single
oxygen atom. The phenyl 2,2’,2"-nitrilotriphenoxy stannane 9 was made by
Ravenscroft“ for the study of mercuridestannylation of phenylstannatranes. To
our knowledge this is the only reported example of a heavy-metal complex;

unfortunately, the authors provided no structural information for this Species.

(I38H17 \
o s. /
E O , C4H9
N
H25012
H25012 3 C8H17
10a 10b

A search of the literature (CAS Online, Cambridge Structural Database,
Beilstein online, and ISI) revealed only two 2,2’,2”-nitrilotriphenol units
containing additional substituents on the aryl rings. Soulie et al. prepared both
the symmetrically substituted tris(2-hydroxy-5-dodecylphenyl)amine and the
asymmetrically substituted (5—butyl-5’-dodecyl-5”-octyl-2,2’,2”-triphenol)-amine.
These two compounds were used to synthesize tetrasubstituted
tribenzosilatrane 10a“ and 10b“. These same authors in 1993 reported the X-
ray structure of tris(2-methoxyphenyl)amine 1117 which had already been solved

and reported by Miller et al. in 1989.18

1.3. Phenoxide Complexes of Lanthanides
The second body of reference literature centers on lanthanide complexes.
A huge number of lanthanide alkoxides complexes are known. Many of these
complexes tend to be polymeric and insoluble in most solvents. The systems

most relevant to the present work are phenoxide complexes, particularly those

dimeric or oligomeric complexes that display magnetic interactions between

lanthanide centers.

Two catecholate systems reported by Freeman et al.19

are of interest in
that they are soluble at extremely alkaline pHS (>11). Generally, Lanthanides
tend to precipitate out of solution as hydroxides at such high pH values. These
particular complexes, Na5[Gd(cat)4]-21H20 12 and Na5[Gd(cat)3]2-20H20 13, are
polyanions in which the catecholates directly coordinate and encapsulate the

lanthanide, excluding solvent molecules from the lanthanide ligand sphere. For

the Na.[Gd(cat)a]2-20H20 13 species, the polyanionic dimer units are linked

I— —-6

— — -5
° 8003C
6Na
0

4 \Gd Gd\

12 13

+

 

 

 

 

through sodium and water molecules to form Chains. The Gd-Gd distance in this
phenoxy-bridged dimer is 3.84 A. Unfortunately, magnetic data on these

complexes were not reported.

20
I

Orvig eta. reported interesting lanthanide N403 amine phenoxide ligand
complexes that show no solvent interaction in the first lanthanide-ligand bonding

sphere. The 1:1 gadolinium-(amine phenol ligand) Complex 14 is a neutral,

phenoxy-bridged dimer with a Gd-Gd distance of 3.98 A. This heptadentate

lanthanide complex is stable under

basic to weakly acidic conditions in . / \
H O 0

both solid and solution forms. N .

Magnetic studies on 14 Showed

/ \ /' H
evidence ofaweak antiferromagnetic (N Gd\ Gd \

 

 

 

H /
Gd-Gd coupling (J=-0.045cm"). 0
Panagiotopoulos et al.”, 2 H
reported two acetate-bridged 14

lanthanide dimers, [Ln2(CH3002)e(phen)2] where phen is o-phenanthroline and
Ln is cerium or gadolinium. Both complexes demonstrated antiferromagnetic
coupling; however, only the structure

of the cerium complex 15 was

 
 
 

reported. The cerium complex showed g“.
a Ce-Ce bond distance of 4.035 A,
and an antiferromagnetic coupling
constant of J=-0.75 cm". The Gd-Gd
complex was reported to have an antiferromagnetic coupling constant of J:-
0.053 cm'1 with the expected Gd-Gd bond distance equal to or less than that in

Ce-Ce complex.

Guerriero, et al., 22 synthesized various lanthanide complexes with acyclic

Schiff bases. Of particular interest is the homo-dinuclear gadolinium-Schiff base

complex 16 which Shows a
large antiferromagnetic 0
coupling constant (J=- N O O

-1
0.24cm ). The complex I-bC(CH2)11—N—Gd Gd (N03)2 4l-I20

contains two gadolinium
O

atoms bound in the same

ligand by two phenoxy 0

groups. Although the 16

structure of the complex is not known, the authors proposed that the large J
value results from a superexchange phenomenon through the bridging atoms.
However, the absence of large coupling constants in other phenoxide bridged

complexes conflicts with this explanation.

Costes, et al., like Guerriero, synthesized lanthanide complexes with
tris(4-(2-hydroxy-3-methoxyphenyl)-3-aza-3-
butenyl)amine 17.23 They created both the Yb-
La and the Gd-Gd complexes. The latter (©\O/
showed an antiferromagnetic interaction with a N 1'9 OH 3
J=-0.104 cm“. They did not report a structure 17
for the Gd-Gd complex but they speculated that the Gd-Gd distance should be

Similar to the Yb-La distance, which they reported as 3.7337(6) A.

A unique structure was synthesized by Hedinger, et al.“ They reacted

1 ,3,5-triamino-1,3,5-trideoxy-Cis-inositol with lanthanide salts. Their X-ray data

Showed two triply deprotonated ligands encapsulating an equilateral triangle of
lanthanide ions. In the gadolinium complex they measured an antiferromagnetic

coupling J=-0.092 cm".

RESULTS 8: DISCUSSION

2.1. Synthesis of Ligands

 

Two ligands were synthesized and used to form complexes: triol (tris(2-
hydroxyphenyl)amine) 3 and a trinitro analogue (tris(2-hydroxy-5-
nitrophenyl)amine) 18. Triol 3 was prepared according to Frye’s procedure° with
one exception: 18-crown-6 was used as a phase transfer catalyst for the Ullman
reaction25 (Scheme 2.1). This alteration increased the yield to 73%. The
demethylation was performed as reported by Frye and worked in good yield.

Scheme 2.1

K2003, Cu
dichlorobenzene

The triolate (deprotonated triol 3) reacts readily with oxygen. To offset this

 

sensitivity, electron-withdrawing nitro groups were added to the aryl rings. We

attempted to make the tris(2-methoxy-4-nitrophenyl)amine 21, by starting with 2-
methoxy-4-nitroaniline 19. This species was readily converted to 2-iodo-5-

nitroanisole 20 via the diazonium salt.

Scheme 2.2
”3° c 0
NH, Hao—o “03.6“ \0 ”3 ,0 H 0, “3
N + '
dichlorobenzene 0 2
19 20 21 22

The Ullman reaction on this system (Scheme 2.2) was not efficient. When
two equivalents of 2-iodo-5-nitroanisole were used, only the diphenyl amine 22
~35% and reduced 3-nitroanisole ~10% were obtained. With a large excess (>6
equivalents) of the iodo compound, modest yields of the desired compound 21
~30% and diphenyl amine 22 ~30% were isolated. The remaining product was
an unidentified tar-like residue. Unfortunately all attempts to demethylate the
trinitro trimethoxy compound 21 with AlCla, BBra, or 40% HI failed.

Direct nitration of trimethoxy compound 11 or triol 3 resulted in a mixture
of products, each having at least one nitro group para to the central nitrogen.
Some also were nitrated ortho and/or para to the hydroxy group. None of these
products had three equivalent aryl rings. To prevent ortho nitration triol 3 was
acetylated. This did solve the ortho nitration problem, but nitration still took place

meta and para to the central nitrogen.

10

Scheme 2.3

O I 0
Jo T H30" 40 H‘o
N' L Q44 _;“9_"__. o"§;§-—N
3 . adenoid
I°2~ I
23 24 18
To deactivate the ortho, para-directing ability of the central nitrogen, it

N PM

3

 

 

I
L

 

 

 

 

was protonated using trifluoromethanesulfonic acid. Subsequent nitration with
nitric acid in acetic acid resulted in tris(2-acetoxy-5-nitrophenyl)amine 24 (30%)
and a complex mixture of other nitration products. Compound 24 is readily
converted to the trinitrotriolate 18 with NaOH. Compound 18 can be converted to
tris(5-amino-2-hydroxyphenyl)amine-SHCl salt 34 using PdlC and sodium
borohydride.

To make other substituted triols, attempts were made to brominate triol 3
and the trimethoxy compound 11. Only complex mixtures
of substitution products were obtained. Using the same
acetylation and protonation scheme used for formation

of trinitrotriol follow by bromination it was possible to

 

synthesize triS(5-bromo-2-hydroxy-phenyl)amine 25
(bromotriol) 36. The bromotriol was identified by NMR only and was never used
for any complex formation. Exhaustive bromination yielded the symmetric
product 25 (<25%), a hexabromo trimethoxy triphenyl amine. Unfortunately upon

demethylation the resulting hexabromotriol 26 was only sparingly soluble in most

11

organic solvents. Due to the poor solubility and low yield of this reaction, this

direction of study was not pursued further.

2.2. Synthesis of Complexes

Lanthanides in the presence of hydroxides usually make an insoluble
polymeric material. Therefore, we first attempted to synthesize the 1:1
lanthanide triolate complexes in anhydrous acetonitrile using sodium hydride as
a base. This procedure resulted in insoluble solids (later identified as the 1:1
complexes) and dark blue solutions. The blue color might indicate anionic or
polyanionic radical species, but attempts to isolate and purify the blue

compounds were unsuccessful.

Scheme 2.4

 

 

 

Difficulties in the synthesis of neutral 1:1 complexes led us to explore the
charged 2:1 complexes with the general formula NaaLn(triolate)3-nH20-mCH30H.
Addition of a methanolic solution of Ianthanide(lll) chloride to a clear colorless
solution of sodium triolate 27 resulted in a clear solution. But with ratios of
triolate to lanthanide less than 2:1, white precipitates formed corresponding to

the 1:1 complexes. Concentration of the remaining solution led to crystallization

12

of the 2:1 complexes. Using similar procedures, we isolated the lanthanum,
gadolinium, and ytterbium 1:1 (28, 29, 30) and 2:1 (31, 32, 33) complexes.
Attempts to isolate a cerium complex failed. The reaction mixture would
turn dark brown to black followed by the precipitation of unidentified tar. This
result may be due to the ease of oxidation of Ce+3 in the presence of oxy-bases.‘
The smallest trace of oxidant may start a cycle of auto-oxidation where the Ce"
oxidizes the ligand, which after undergoing further changes could oxidize a Ce“3
ion (Scheme 2.5). The radical cation of the ligand is not stable, and its formation

would lead to destruction of the ligand and the formation of tar. No attempt was

made to identify the oxidation products from this reaction.

Scheme 2.5:

Ce+3 + Oxidant ——’ Ce“

L + Ce”4 —> Ce+3 + L "‘
L 0+ I L! 0+
(L’)‘* + Ce*3 ——-> L’ + Ce“

2.3. NMR Analysis

The presence of a strong paramagnetic center hinders NMR analysis of
lanthanide complexes by causing broadening and shifting of the proton signals.
However, lanthanum itself is diamagnetic and does not present this difficulty. In
addition, although ytterbium (s= 1/2 ) is paramagnetic and causes large proton

chemical shifts, it does not broaden and shift signals as much as gadolinium

13

(s=’/,). Therefore NMR can help in the characterization of both lanthanum and
ytterbium complexes.

The NMR spectra seen in Figure 2.1 show the proton Signals in the
triolate 27 shifted upfield from the free triol 3 (not Shown) at 7.0-6.86 ppm, as
expected. When the triolate forms a complex with lanthanum 31, the proton
Signals shift back downfield, consistent with the expected electron density
depletion from the ring. The titration of sodium triolate 27 with lanthanum
chloride in 020, Figure 2.2, shows Clearly that there is a 2:1 complex. At ratios of
less than 2:1, NMR becomes close to impossible because precipitate formation
interfered with the lock signal. The presence of two distinct sets of signals, for
the triolate and the complex, and the fact that lowering the temperature to 5°C
from 25°C Showed no Significant line width or Chemical shift variation of any of
the signals, together indicate that this complex does not undergo ligand
exchange on the NMR timescale.

Titration of the trinitro triolate 37, (triple deprotonated 18) with LaCl3 in
D20 also provided evidence for 2:1 complexation through broadening and
shifting of signals, but there were no distinct free and complexed trinitrotriolate
signals. Attempts to resolve the proton signals by variable temperature NMR to
get complexation rates proved unsuccessful within the accessible temperature
range, but the complexation rate appears to be fast on the NMR timescale. On
the other hand in methanol solution, two distinct sets of signals were observed
which showed no significant line width or Chemical shift variation of any of the

Signals even at -100°C.

14

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”.03 ”252.282
26m

 

16

03 c_ «.0 m4 53> U295 5N 920:.an .0 93on 15.2.1. “No.52“.

Eng m.m vim m.m m.m 5m m.m m6 OK “.5

PL-PrphPPbbPIP PL_-bhblFbrrF—Phrrhblbph—b~be—ybIbhn—P-Db

 

 

 

so; - Ilé<<l- - <<I<<<llll

”.03 65.0382
2mm

 

16

This behavior led us to conclude that in methanol the exchange happens much
slower than the NMR timescale.

A first look at the NMR spectrum of the ytterbium triolate complex 33 in
D20 Showed only two signals at 7.90 and 11.4 ppm, but expansion of the scale
uncovered the other two Signals at 24.5 ppm and at -0.5 ppm. Titration analysis
showed that the Yb complex 33, like the La complex 31, had a 2:1 stoichiometry

and had no appreciable exchange at the NMR timescale.

2.4. Mass Spectrometric Analysis

The stability of lanthanide triolates shown in the NMR studies led us to
examine them by mass spectral analysis. Using negative ion fast-atom-
bombardment mass spectrometry (FABMS), on a recrystallized sample of
complex 31, it was possible to observe the molecular ion of the La(triolate)2
nucleus at m/z 721. This included 2 protons, and had a Charge of -1. Such
protonation is not unexpected, given the hydrogen-rich glycerol matrix used to
volatilize the sample. The peak at rnlz 520.2 is due to the 1:1 complex with one
monodeprotonated glycerol attached, while the peak at rnlz 446.1 corresponds
to the 1:1 complex with a hydroxide attached. From these data, it is not clear if
there is a mixture of 1:1 and 2:1 complexes in the matrix, or if these two peaks
are fragmentation products of the 2:1 complex. It might be possible to test the
latter case using tandem mass spectrometry to isolate the molecular ion peak,

but we did not have the opportunity to conduct such an experiment.

17

2.5. X-ray Structures

Crystals of the 1:1 complexes of lanthanum 28 and gadolinium 29, and 2:1

complexes of gadolinium 32 and ytterbium 33 have been analyzed by X-ray

diffraction. Selected geometrical data are compared in Table 2.1

Table 2.1: Bonds and Angles of Lanthanide Triolate Complexes

 

 

 

 

 

 

 

 

 

 

La1:128‘ Gd1z129 Gd2:132 Yb2:133"
Ln-Ln 3.974(3) 3.8719(8) 7.802(5) 7.744(1) 7.842(1)
Ln-OPh‘ 234(2) 240(2) 2.239(3) 2.353(7) 2.322(8) 2.298(8)
237(2) 247(2)‘ 2.311(3) 2.384(8) 2.283(7) 233(1)
257(2)‘ 244(2) 2.338(3)‘ 2.401(8) 2.289(9) 2.293(8)
bridging OPh 244(2) 266(2) 2.361(3)
average Ln-OPh 2.44 2.49 2.312 2.37 2.30
Ln-DMSO 264(2) 258(1) 2.385(3)
258(2) 285(1) 2.372(3)
257(1)
bridging Ln-DMSO 288(1) 272(1)
average Ln-DMSO 2.618 2.623 2.369
Ln-N 280(2) 292(2) 2.630(4) 2.887(9) 288(1) 288(1)
pyramidalization anglea 104.2 105.7 104.2 105.4 104.9 104.9
N-Ln-N angle 180.8(4) 158.9(2)
ring twist ring 1 57.8(9) 74.4(7) 83.8(2) 52.9(5) 80.8(5) 74.0(4)
61.7(6) 66.4(7) 58.5(2) 71.4(5) 75.8(4) 59.5(5)
70.9(8) 57.3(9) 70.6(2) 59.5(4) 53.4(5) 52.8(4)

 

 

 

 

 

aFirzst column refers to La(triol) with Cordination Number (CN)=8 second column La(triol) CN=9; ”
columns represent different tn'olate caps; cListed in order of increasing label number, ' indicates

bridging OPh; d Pyramidalization angle is defined as 90+sin“( average CN distance /

Displacement of N from CCC plane)

18

Crystallographic data for these compounds can be found in Tables A1 -4, while
their fractional coordinates and anisotropic displacement parameters are given
in Tables A5-12 in the Appendix. Drawings with atom-labeling schemes are
given in Figures A5-A8. Examination of the 2:1 complexes of gadolinium 32 and
ytterbium 33 crystals was incomplete, because, in each case the crystal fell off
the sample mount 2/3 of the way through the data collection (Extreme building
vibrations caused by construction occurred over the 2-3 weeks of data
collection.) Fortunately, the remaining data sets were of sufficient quality to yield
reasonable structures, but refinement of the thermal parameters using full-matrix
least-squares on either F or F2 resulted in some non-positive—definite atoms.

As expected, the X-ray data pointed to two unique structural motifs,
corresponding to the 1:1 and 2:1 complexes. The 1:1 complexes exist as dimers
with the triolates bridging two lanthanides in the crystal. These are isolated
dimers with no close intermolecular contacts or any uncoordinated solvent
molecules in the structure. The 2:1 structures consist of a core lanthanide
triolate "sandwich", one lanthanide capped with two triolates. The sodium
counterions connect these trinegative ions into parallel chains, with all the
metals in the same plane.

The 1:1 lanthanum and gadolinium complexes (Figure 2.3) Showed a
dimer structure similar to the aluminum complex 6a. The lanthanum complex is
asymmetric with coordination numbers (CN) 8 and 9 at the two distinct

lanthanum centers.

19

m~ 829.298.8589 8:8 mm 828.298.8585 .8 852,95 ngo a." 2:9...

ON mu
, ..\.. - ... . {I ,
llxfi C\ I ’ fl! \ /..
/. , \,. .I ._\

P . . i
A 54‘ .
//\./1\.\W.\. K /\, e.. 2.

...l.\\ . ,
o. .24 f :29: ......

\

 

20

The two lanthanum ions are 3.974(3) A apart; each is capped by a triolate
ligand. One phenoxide oxygen atom from each ligand and one oxygen atom from
a DMSO molecule form a threefold bridge between the two metal centers. The
remaining sites on the La centers are filled with three DMSO molecules on one
La and two on the other. The average La -OPh distances are 2.44 and 2.49 A
respectively, with the longer distance found on the 9-coordinate La center. This
is comparable to the La—OPh distances reported by Freeman et al.19 in their
gadolinium catecholate dimers 13. The central nitrogens are pyramidalized
inward with pyramidalization angles (90 + sin'1 (average CN distance I
displacement of N from the CCC plane, planar = 90°) of 104.2 and 105.7
respectively, with the larger angle found on the 9-CDordinate La center. Stoudt et
al.26 reported similar pyramidalization in tris(2-alkoxyphenyl) amine complexes
with sodium and potassium. Each ligand cap has a pseudo-03 symmetry with a
ring twist angle (the mean angle of aryl ring planes out of the central nitrogen’s
three-carbon plane; coplanar = 0.0 °) of 57.6(9), 61 .7(6), 70.9(8) and 74.4(7),
66.4(7), 57.3(9). The La-N distances are 280(2) and 292(7) A, significantly
longer than other amine-La complexes in the literature. This long La-N distance
may result from the larger lanthanum ion not fitting in the pocket or the fact that
oxygen ligands have met the coordination requirements of the lanthanum ion
and the non-basic nitrogen does not have much to offer in addition.

The Gadolinium 1:1 complex 29 has a similar structure to the lanthanum

1:1 complex 28, except that it is symmetric, with a point of inversion between the

two metal centers. Each Gd has a CN of 7. There are two triolate ligands, each

21

capping a gadolinium, with one of the phenoxides of each ligand bridging the two
metal centers. The remaining sites on the gadolinium centers are filled with two
DMSO molecules. The average for all Gd-OPh distances is 2.31 A. This distance
is Shorter than in the lanthanum complex aS expected, considering the smaller
Size of the gadolinium ion. The Gd-Gd distance is 3.8719(8) A, Shorter than 3.98
A found by Liu et al. in their phenoxylate bridged dimer 14.27

The Gd 2:1 and Yb 2:1 complexes 32 and 33 have a core where the
lanthanide is encapsulated between two triolates with no solvent oxygens coming
close to the central metal. In these complexes the triolate acts as a tetradentate
ligand with the central nitrogen also complexing the metal. These trianionic
lanthanide sandwiches are connected in chains through the charge balancing

sodium ions and solvents of crystallization.

 

Figure 2.4: Core structure of Nang(triolate)2-2HZO-GCH30H 32 Clearly
showing the diaratrane cage.

The sandwich complex Shown in Figure 2.4 has the triolate caps off-center

resulting in a N-Gd-N angle of 160.8(4)°; the Yb complex 33 has a Similar

22

structure, with a N-Yb-N angle of 158.9(2)°. A similar offset of 154.5° has been I
reported by Stoudt et al. in their sodium tetraphenylborate salt complex with
trimethoxytriphenyl amine 11.23 For gadolinium and ytterbium complexes 32 and
33 respectively, (see Table 2.1), the average Ln-OPh distances are 2.37 A and
2.30 A; For Gd and Yb complexes 32 and 33 respectively, the average Ln-OPh
distances are 2.37 and 2.30 A; the Gd complex 32 has a CZ axis through the Gd
center; the triolate-Ln cages have pseudo-Ca symmetry with ring twists angles of
52.9(5)°, 71 .4(5)°, 59.5(4)° for Gd complex 32 and 60.8(5)°, 75.8(4)°, 53.4(5)°,
74.0(4)°, 59.5(5)°, 52.8(4)° for Yb complex 33; and the central nitrogens are
pyramidalized inward with pyramidalization angles of 105.4° in the Gd complex,
and 104.9° and 104.9° in the Yb complex (see Table 2.1).

As Shown in Figure 2.5 the extended structures consist of chains of
lanthanide triol sandwiches connected through sodium ions. The sandwiches
alternate opening slightly to the outside of the chain, left and right. There are
three sodium ions in a line between each sandwich. The central sodium ion is
connected to one phenoxide of each sandwich. All the metal ions (Na+ and
lanthanide) in a single Chain lie in the same plane. In the end-on view (Figure

2.6) one can see that the Yb 2:1 complex 33 has a slight twist to the Chains.

23

Gd 2:1 complex 32

Na I .
Q
Yb 2:1 complex 33
O
o 0 , ...
0 ° ‘ ”‘1'
Na .
Na? , .4 ‘ ,Yb "3
X5014. W.’ .'.'
o ‘ v, . .
Na / . ‘ “.Na Na .
Na . o ’ O
(a
0

Figure 2.5: Views perpendicular to the metal-containing plane of
NaaGd(triolate)z-2H20-60H30H 32 and Na3Yb(triolate)2-2H20-5CH30H 33
(carbon and hydrogen atoms are omitted for clarity).

24

Gd 2:1 complex 32

YD 2:1 complex 33

AIMS 0&J
“43V 0 0 .
6.x. A.)
CPI“. Mn”
8 A?
o o «USU

Figure 2.6: End on views of NaaGd(triolate)2-2H20-6CH30H 32 and
NaaYb(triolate)2-2H20-50H30H 33 (carbon and hydrogen atoms are

omitted for clarity).

25

2.6. Magnetic Studies

Magnetic susceptibility measurements in the temperature range from 1.8
K to 300 K and -200 G to 50 kG were performed on a MPMS Quantum Design
SQUID magnetometer., Figure 2.7 Shows the temperature dependence of the
magnetic susceptibility’s, displayed as the product ()(T), for the 2:1 and 1:1
complexes of Gd and Yb. The Gd 2:1 complex 32 has a steady xT of 7.5 cm3 K
mol'1 between 300 K and 70 K. Below 70 K, )(T increases slightly to a value of
7.85 cm’ K mol'1 at 10 K and then more rapidly to a maximum of 8.12 cm3 K mol'1
at 5 K. Below 5 K xT decreases to 7.5 cm3 K mol'1 at 1.8 K. This low temperature
rise could result from ferromagnetic coupling in the chains. If this is true
however, the coupling would be extremely small. More data are needed to verify
that this is a real magnetic phenomenon. The decrease below 5 K could be a
result of antiferromagnetic coupling between the gadolinium ions.

The Yb 2:1 complex 33 shows a steady decrease in xT from 1.36 cm3 K
moI'1 at 300 K to 1.27 cm" K mor1 at 10 K. Below 10 K, )(T increases to 1.43 cm°
K mol'1 at 1.8 K. This behavior may result from ferromagnetic coupling in the
chains, but the complexity of the magnetic behavior of Yb limits realistic
speculation as to the nature or mathematical fitting of the interactions. Similar to
the Yb 2:1 complex 33, the Yb 1:1 complex 30 shows a steady decrease in )(T
from 3.17 cm" K moI" at 300 K to 2.3 cm° K mor1 at 8 K. Below 8 K, xT
decreases sharply to 1.8 cm3 K mol'1 at 1.8 K. This decrease is suggests modest
antiferromagnetic coupling, as might be expected when two paramagnets are

placed in close proximity. A final note on the Yb complexes is that the room

26

.mu 3 8 Lo. E 88.8.8.8 I 8 Ion:o9of~ho§o§o>noz 2 ”on 0mzov.~§o_o§~o>$
an Ion:8.0":398.2588onV an owzovhegoéwooi 8.. 3828 P 9, Ex Eu 2:9“.

8a com com 3. 3.: 8. on. o

 

 

 

 

 

 

 

2. 2 . .
_ w .
_ _ . .
m _ X X X X X X X X i
X X X
*3le IXII XII #Zx- IIXI x1 1.x. ..x x x x x x 1* III I M . 1.. .
_ +++++
+ + + + + + + + + + + + + + + +++ m
A.- + + + + .
. . .
IIII (I E -..- III! -.I! II- I. I I .......... - I... l
_ e. m e
. .
I I .iAriII II I I I I a n I. III. .IIII.TI I... .. II-I . . m. . i w l
. .
_ _ ” \QIJI
a a e 4. D D D u D m...
..llrIII-.I I- ITIIIIIII . - I... I- - I- II III - B D: Dhbfl: m M
w
m n moi
” ...
. .. ..- I. -IIIII- IL - - e.
.
.
..IIliIIf .I...III.IIII.IIIIII.III...l.IIII.I:IIIIII.I.I-I.I.IIIII _—- ...- ....IIl .. IIIIIIIII IT..- .-.. II-.. - £12....“ - i . ...I-.. ...II. .. NW
I.---IIIfi.I|Ii-I. .l-I.-l..., . .. .. -. --. .--.. , .- i. , --.- -. .-.. V—

 

 

 

 

 

 

o.

27

temperature )(T values are approximately one-half of the theoretically predicted
values using the free-ion approximation 2.57 and 5.14 cm3 K mol'1 for the 2:1
and 1:1 complexes, respectively. These numbers however, are based on an
assumed formula Nang(triolate)2-2H20-5CH30H and (Yb-Triolate)2-4DMSO.
These formulas are obtained from the X-ray structures; no elemental analyses
were done.

The Gd 1:1 complex 29 shows a )(T of 15.8 cm3 K mol‘1 at 300 K which is
quite close to the free-ion predicted value of 15.76 cm3 K mol". The value of XT
decreases slowly to 15.6 cm3 K mol’1 at 50 K. Below 50 K there is a progressive

decrease to 9.15 cm3 K mol'1 at 1.8 K. Gadolinium has a 88 ground state which
allows an expression to be derived for the magnetic susceptibility using the
Hamiltonian H=J S182.

_WS,j
kT

ZS(S+1)(2S+1)o,e[—T]

 

 

 

 

 

2.,- = - _ W - 1012504881289
’ I—‘ ”I
T, Z(ZS+1)QSe "T’
S
g=2 W3.) =J,(S(S+1)—ZS(S+1)
s=7/2 (as =2.s‘+1—S
S=2s,23—1, ..... O (25 =ws —a)(S+,)

Equation 2.1: Equation for the magnetic susceptibility of two coupled S=7l2
ions.

28

This model has two 7/2 spins coupled antiferromagnetically where J is the
coupling constant. A least squares fit of the experimental data using Equation
2.128 yields an antiferromagnetic coupling constant J=-0.058 cm'1 and g=2.0.
Table 2.2 lists coupling constants for gadolinium dimeric systems. From the
literature data it can be seen that our J=-0.058 cm'1 is in the lower range. This is
comparable to J=-0.053 cm'1 determined by Panagiotopoulos et al.19 in the their
acetate-bridged Gd complex, but is higher than the J=-0.045 cm'1 reported by Liu
et al.18 One thing to note is that Liu’s phenoxide-bridged complex has a longer
Gd-Gd distance (3.98 A) than the 3.87 in our Gd 1:1 complex 29. It would be
expected that the shorter Gd-Gd distance would result in stronger magnetic
coupfing.

Table 2.2 Magnetic coupling constants for gadolinium dimer complexes.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bridging atom type Gd-Gd (A) J (cm"’/ 9 Ref.
Carboxylate (system has zn*'f 4.2515(2) -0.042 I 2.0 29
ions in the structure) A
Phenoxy 3.98 -0.045 I nla 20
Acetate <4.0 0.053 I nla 21
Phenoxy (Gd 1:1 29) 3.8719(8) -0.058 I 2.0
Alkoxy (three Gd ions in 3.730(2) -0.092 / 1.98 24
equilateral triangle)

Phenoxide (schiff base) nla -0.104 I 1 .999 23
Phenoxide (schiff base) nla -0.140 - -0.082 30
I nla
isophthalate nla -0.18 / n/a 31
isophthalate nla -0.19 / nla 32
Alkoxy 3.7643(7) -0.198 I 1.975 33
isophthalate n/a -0.21 /n/a 34
Phenoxy (schiff base) 3.6353(2) -0.22 I 1.93 35
Phenoxy (schiff base) n/a -0.240 I nla 22
Benzoate nla -0.471 / 1.975 36

 

 

 

 

 

29

In summary, triol 3 and trinitrotriol 16 react with LnCla in the presence of
sodium hydroxide to form 1:1 and 2:1 complexes as Shown by the crystal
structures of complexes 28, 29, 30, and 31 and NMR analysis of complexes 31
and 33. Magnetic studies of the Gd 1:1 complex 29 have shown antiferro-
magnetic coupling between the gadolinium ions with J=-0.058cm". This weak
coupling is typical of dimeric lanthanide complexes, due to the small radial
extent of the magnetically active f orbitals. It suggests that the coupling between
more widely separated centers would quickly become negligible, in agreement
with the magnetic data for the 2:1 complexes, which Show at most hints of
coupling. TheSe findings cast doubt on the potential of lanthanide triolate
complexes as building blocks to make extended magnetic structures. On the
other hand, the presence of the triply sodium-bridged chains in the 2:1 complex
suggest that such complexes with other, more strongly interacting, paramagnetic
metals might develop nontrivial intercluster coupling, as seen in the work of
Misiolek, et al. from this research group.37 Trinitrotriol 16 shows promise as a

stable, oxidation-resistant ligand, and merits further investigation.

30

EXPERIMENTAL

Figures 2.3 and 2.4 are presented in color.

3.1. Equipment and Chemicals used

All manipulations were performed either in a glove bag continuously
purged with N2 or on a low vacuum Schlenk line that pumped to 1 torr and was
directly attached to an argon tank with no scrubbing columns for deoxygenatlon.
Solutions were purged with N2 or argon for at least 10 min. Glassware was
generally soaked in a base bath (NaOH isopropanol) for at least one day, then
rinsed with deionized (DI) water, dipped in an acid bath (aqueous 5-10% HCI),
rinsed with DI water and then acetone, and allowed to air dry. All Chemicals were
reagent grade and were purchased from Aldrich. Melting points were determined
on a Thomas-Hoover apparatus and are uncorrected.

Routine 1H and 13C NMR spectra were obtained at 300 and 75 MHz,
respectively, on Varian GEMINI 300 or VXR-300 spectrometers; the latter
instrument was used for all variable temperature (VT) analysis. 1H NMR shifts
reported herein are referenced to residual 1H resonances in deuterated solvents:
acetone-d6 (5 2.04 ppm); CDCI; (5 7.24 ppm); 020 (5 4.66 ppm); and methanol-
d. (5 3.30 ppm for the 00;. group). The 13C shifts are referenced to those of the
deuterated solvent CDCI3 (5 77 ppm) and methanol—d4 (5 49 ppm). Peak
multiplicities are abbreviated: s, singlet; d, doublet; t, triplet; dd, doublet of

doublets; m, multiplet.

31

3.2. Synthesis:
3.2.1 . Ligands
Hacb Tris(2-methoxyphenyl)amine 11 was prepared using Frye’s

( 3N procedure6 except that 18-crown-6 was used as described below. A
500 ml three-neck round-bottom flask fitted with a mechanical stirrer was
charged with 12.3 g (0.1 mol) of anisidine, 51 g (0.22 mol) of 2-iodoanisole, (100
g, 0.72 mol) of K2003, 28 g (0.44 mol) of electrolytic copper and 5 g (0.019 mol)
of 18-CTown—6. After the addition of 200 ml 1,2-dichlorobenzene the flask was
fitted with a condenser. The reaction was allowed to reflux for 48 hours, after
which TLC showed complete conversion to the triarylamine 11. The reaction was
allowed to cool to room temperature and was taken up in chloroform. The solid
was filtered off, and the chloroform and 1,2-dichlorobenzene removed by rotary
evaporation, resulting in a brown-black tar. Addition of 100 ml acetone, followed
by cooling overnight, led to precipitation of a white solid, which was filtered off
and recrystallized from ethyl acetate. Several crops yielded 24.3g (73%) of
product with mp 142-1435 °C uncorrected (lit. 145-147 °C)°; H-NMR in CDCI3;
5(ppm) 7.0 (m, 3H), 6.85-6.75 (m, 9H), 3.55 (s, 9H); 13C-NMR in CDCI3 5(ppm)
153.1, 137.7, 124.5, 123.7, 120.6, 112.6, 55.7. ElMS rnlz 335(M‘).

H‘O Tris(2-hydroxyphenyl)amine (trial) 3 was prepared by dissolving

 

3” 18.4 g (55.2 mmol) of tris(2-methoxyphenyl)amine 11 in 100 ml
toluene in a 500 ml round-bottom flask to which 25 g (188 mmol) of AlCl3 was
then added. The mixture was refluxed for 4 hours. The mixture was quenched

with 150 ml of 10% aqueous HCI, resulting in the precipitation of a gray-white

32

solid. This material was collected by filtration and recrystallized from methylene
chloride to give 6.7 g of triol 3. Additional product was recovered from the
toluene layer by removal of the solvent under vacuum. The resulting brown solid
was recrystallized from toluene. The two batches were combined after checking
purity by NMR and recrystallized from toluene for a final yield of 11.2 g (76%) of
triol. mp. 167.5-168.5°C (lit.171-174°Cs): ‘H-NMR in CDCI3 5(ppm) 7.09 (td, 3H),
6.86 (td, 3H) 6.94 (dd, 6H) 13C-NMR in CD3OD 5(ppm) 152.48, 136.98, 126.70,
126.17, 120.94, 117.41 ElMS mlz 293 (M’).

Hac‘o TriS(2-methoxy-4-nitrotriphenyl)amine 21. 2-Methoxy-4-nitro-

02N 3" ~ aniline 17 50 g (0.3 mol) was converted to 2-iodo-5-nitro-anisole

 

18 using a standard literature procedure?“3 A 250 ml three-neck round-bottom
flask fitted with a mechanical stirrer was charged with 1.68 g (10 mmol) 2-
methoxy-4-nitroaniline 19, 16.8 g (60 mmol) 2-iodo-5-nitro-anisole 20, 10 g (72
mmol) K2003, 2.8 g (44 mmol) electrolytic copper and 0.5 g (1.9 mmol) 18-
crown-6. After addition of 50 ml 1,2-Dichlorobenzene the flask was fitted with a
condenser. The reaction was allowed to reflux for 3 days, after which TLC
showed no more starting compounds. The reaction was allowed to cool to room
temperature and was extracted with chloroform. The solid was filtered off, and
the chloroform and 1,2-dichlorobenzene removed by rotary evaporation,
resulting in a yellow-brown-black tar. The product were purified on a silica gel
column using ethyl acetate/hexane (1 :1) as solvent. The first compound to come
off was 3-nitroanisole. The first yellow product (~30%) was bis(2-methoxy-4-

nitrophenyl) amine 20. 1H-NMR 5 (ppm) 7.93 (dd, 1H), 7.79 (d, 1H), 7.48 (d, 1H),

33

The second yellow product (~30%) was tris(2-methoxy-4-nitrotriphenyl) amine
21. mp 191 -1 95 °C uncorrected. 1H-»NMR in CDCI3 5 (ppm) 7.79 (dd, 3H), 7.78
(s, 3H), 6.90 (d, 3H), 3.65 (s, 3H). ElMS mlz 470 (M’)
o Tris(2-acetoxyphenyl)amine 23. Triol 3 6.0 g (20.5 mmol) was
N dissolved in 10 ml pyridine and 20 ml acetic anhydride. This mixture
was refluxed for 2 hours. Ether (40 ml) was added, and the solution
extracted with aqueous CuSO. until no more pyridine complex was visible as
indicated by the lack of color change in the CUSO4 layer. The ether was then
removed under vacuum, resulting in 8.4 g (98% yield) tris(2-acetoxyphenyl)

amine 21, mp 130-132°C (lit.133-135)°. 1H-NMR in coaoo 5 (ppm) 7.05 (m,

12H), 1.67 (s, 9H). 13C-NMR in CD300 5 (ppm) 168.7, 144.1, 138.7, 126.6,

126.4, 124.2, 123.8, 20.0
TriS(2-acetoxy-5-nitrophenyl)amine 22.

° Tris(2-acetoxyphenyl)amine 21 (2.0 g 4.8 mmol) was dissolved in
20 ml acetic acid. Trifluoromethanesulfonic acid 1.5 ml (17 mmol)
was added. In a separate flask, 5 ml concentrated nitric acid was

dissolved in 10 ml acetic acid. Both solutions were cooled in an ice bath. The

nitric acid solution was added dropwise to the triacetate solution over 20 min. A

light yellow solid formed. The reaction was warmed up to room temperature and

stirred for 1 hour, then 50 ml water was added and the yellow solid extracted
with 3 times 50 ml portions of ether. After removal of the ether, the product was

purified using a silica gel column. The third main yellow product from the column

was identified as tris(2-acetoxy-5-nitrophenyl)amine 22, 0.87 9 (Yield 33%) mp

34

204-205 °C uncorrected. 1H-NMR in CDaoD 5 (ppm) 8.18 (m, 6H), 7.36 (d, 3H), I
1.82 (s, 9H). ElMS rnlz 554 [M’]. Note the other components were not positively
identified but the complexity of their NMR spectra suggested an array of aryl ring
substitution patterns.

Tris(2-hydroxy-5-nitro-phenyl)amine 18. Tris(2-acetoxy-5-

nitrophenyl)amine 24 (0.5 g 0.9mmol) was refluxed for one hour in

 

10 ml 0.45M NaOH in methanol. The reaction mixture was a deep
black-purple color. The reaction mixture was neutralized using 1M HCI, and an
orange solid precipitated. This solid was collected and washed with water. No
further purification was needed. Yield. 0.389 (98% yield) mp 256-258 °C 1H-NMR
in Da-acetone 5 (ppm) 7.73 (m, 6H), 7.12 (d, 3H), 3.8 (s,3H)
Tris(5-amino-2-hydroxyphenyl)amine-3HCI salt 34. Trinitro triol

18 (216 mg, 0.505 mmol) was dissolved in 8 ml of 2M NaOH under

 

N2. 15 mg Pd/C 10%, 400 mg (10.5 mmol) NaBH4, and 10 ml H20
was added to a 40ml Schlink flask. The nitro triol solution was slowly added over
a 10 min period. The reaction was stirred for another 30 min. The reaction
mixture was then acidified, and the PdlC filtered off. Adjusting the pH to ~7
resulted in the precipitation of a gray solid that was collected by filtration and
was dried under vacuum. A small portion of this solid was dissolved in dilute HCI
and allowed to dry, leaving the HCI salt 34. (note: the NMR showed no other

products) 1H-NMR in 020 5 (ppm) 6.85 (d, 3H), 8.78 (dd, 3H), 8.90 (d, 3H)

35

Hac‘o Tris(4,5-dibromo-2-methoxyphenyl)amine 25. Tris(2-methoxy-

(Br N phenyl)amine 11 (200 mg, 0.60 mmol) was dissolved in 10 ml

at a acetic acid. After the addition of 3 ml Br; the reaction was refluxed
for 5 hours. A white solid formed and was filtered off, and identified as 25. Yield
not recorded. mp 278 (decomposes). 1H-NMR in CDCI3 5 (ppm) 7.35(s, 3H), 6.98
(s, 3H), 3.55 (s, 9H) (note: this spectrum show the presence of some other
bromination products.) ElMS ”/2 803, 805, 807, 809, 811, 813, 815 [M’].

n‘o Tris(4,5-dibromo-2-hydroxyphenyl)amine 26. Tris(4,5-dibromo-

(8' N 2-methoxy-phenyl)amine 25 (100 mg, 0.123 mmol) was dissolved

at 3 in 10 ml toluene, and 0.2 g (15 mmol) AICI3 was added this mixture
was refluxed for 3 h, then 10 ml 10% aqueous HCI was added. Filtration gave a
white solid, which was almost insoluble in most organic solvents. Acetone did
dissolve it enough to get a NMR spectrum. 1H-NMR 5 (ppm) 7.22 (s, 1H) 7.19 (s,
1 H) OH 5.6 (~1 H).
Tris(5-bromo-2-acetoxy-phenyl)amine 35.

Tris(2-acetoxyphenyl)amine 23, (200mg, 0.47 mmol), was dissolved

 

in 8 ml acetic acid, and then 0.1ml (1.0 mmol) trifluoromethane-
sulfonic acid was added. A solution of Brz (0.2 ml) in 2 ml of acetic acid was
added to the triacetate solution at 0°C. This mixture was allowed to warm up to
room temperature and stirred for 1 hour. A white solid precipitated. The liquid

was decanted, and the solid was washed with cold acetic acid and dried under

36

vacuum overnight. Yield was not determined. 'H-NMR 5 (ppm) 1.75 (s, 9H), 6.91
(dd, 3H), 7.25(m, 6H).
Tris(5-bromo-2-hydroxy-phenyl)amine 36 Tris(5-bromo-2-acetoxy-

phenyl)amine 35, (100 mg, 0.15 mmol) was placed in a Schlenk flask

 

under an atmosphere of N2. To this was added 5 ml degassed 0.45M
NaOH in methanol. This mixture refluxed for 30 min. The reaction was acidified
with 5 ml of degassed 10% HCI, resulting in the precipitation of a white solid.
The solid was extracted with ether. Yield was not determined. 1H-NMR 5 (ppm)

5.7 (br, 3H), 8.75 (d, 3H), 6.98 (dd, 4H), 7.06,(d, 3H).

3.2.2. Complexes
In the preparations of all complexes special efforts were made to exclude any
air. Failure to do so resulted in the complex solutions turning black. All solutions
were purged with dry N; for at least 10 minutes.

Q” j? Ln(triolate)-nDMSO (Ln = La 28, Gd 29, YD 30; n=6,4,4).
N
/°\ 2 Triol 3, 300 mg (1.02 mmol) was dissolved in 3.2 ml of

 

§\ /
©1146 ..omso 0.97M NaOH (3.1 mmol) in methanol. This solution was
2

 

added to the appropriate LnClaotzo (x=7,6,6) lanthanide
(1.0 mmol) salt in 18 ml of methanol. A precipitate formed immediately on adding
the triolate 25 solution. The reaction was refluxed for 2 h, and then the solid was
collected. The solid was dried under vacuum for at least 8 hours. Yields
generally were approximately 80%. This 1:1 lanthanide-triolate complex was

dissolved in 10 ml refluxing DMSO. On cooling, a white crystalline solid formed,

37

which was filtered and washed with cold DMSO and then dried under vacuum for
1 hour. Yield of the DMSO solvated complexes were generally greater than 80%
The Yb complex 28 was speculated to have 4 DMSO molecules based on
thermo-gravimetric analysis kindly performed by the research group of Dr.

Baker, which showed two losses corresponding to two DMSO molecules each.

. O ‘4 Na3(Ln)(triolate)2-2H200xCH30H (Ln = La 31, TD 37,
@849 -
o\§ o 2 Gd 32, YD 33; x=6,6,5,5) Triol 3, (300 mg, 1.02 mmol),
L.

 

aNa‘
was dissolved in 10 ml methanol and 3.2 ml 0.97M

h
0 §\O
<6 to
2 4 NaOH (3.1 mmol) in methanol was added. To this

solution was added 0.5 mmol lanthanide salt in 5 ml of methanol. This reaction

 

 

 

L

mixture was refluxed for 3 h. Note that complexes of the heavier lanthanide do
not completely dissolve in this amount of methanol so 5 to 10 ml more methanol
was added at reflux to form a Clear solution. On cooling, needle-like crystals
formed, in all cases except for lanthanum. The lanthanum complex formed only a
microcrystalline solid. The solids were filtered and were not dried because they
disintegrated when not in a saturated atmosphere of methanol. Yields generally
were >90%, except for the lanthanum complex, which formed in approximately
70% yield.

Na3(La)(trinitrotriolate)2 38. A solution of 100 mg (0.233

mmol) of trinitrotriol 18 was placed in a 25 ml volumetric

 

3Na°

flask. 0.75 ml (3.1 mmol) of .97M NaOH in methanol was

_02N
o i\o
‘Q added. Methanol was added to make 25 ml of solution (9.3
021 2 ~02
_ J

 

 

38

mM). The solution changed from an orange to a deep purple as the NaOH was
added. A 30 mg (85 mmol) sample of LaClaoBHZO was dissolved in 2 ml
methanol. A 20 ml Schlenk flask was charged with 18.4 ml (171 mmol) of 9.3 mM
trinitrotriolate solution. To this Schlenk flask was added the LaCla solution. Upon
addition the purple solution turned back to yellow. The methanol was removed
and a red brown solid was isolated. Yield was not determined. 1H-NMR 6 (ppm)

7.58 (d, 1H), 7.75 (dd, 1H), 7.87 (d, 1H)

3.3. lR

The solid complexes appeared to have some stability in air so IR samples
of La 1:1 28, Gd 2:1 32, Yb 1:1 30, and trisodium triolate 27 were prepared in air
by grinding 1-5 mg of sample with approximately 100 mg KBr and pelletized in a
manual press. The FTIR spectra were obtained on a Nicolet lR/42. Data were
collected from 4000 cm'1 to 400 cm'1 at room temp and under N2. Selected

spectra are presented in the appendix (Figures A1 -A4).

3.4. NMR Studies

Sodium triolate 27 was titrated with lanthanum chloride in D20. A 1.0 M
NaOD solution was prepared by placing 46 mg sodium metal in a 2 ml volumetric
flask and adding cold 020 to the 2 ml mark. Triol 3 (2.3 mg, 0.0078 mmol) was
placed in a NMR tube and 0.5 ml 020, 24.9 uL NaOD (1.0M, 0.030 mmol, 3.8
eq) was added. A stock solution was made by dissolving 8.5 mg (0.024 mmol)

LaCl3-6H20 in D20 to make 1 ml of solution. LaCla solution was added in 2 uL

39

aliquots until 20 pL had been added, after which the precipitate present

interfered with the lock signal. NMR spectra were take after each addition.

3.5. SQUID Measurements

Magnetic susceptibility measurements in the temperature range from 1.8
K to 300 K and -200 G to 50 kG were performed on a MPMS Quantum Design
SQUID magnetometer. Powdered or microcrystalline samples were weighed and
placed in a “baggie" (a piece of DOW Ziploc bag heat-sealed to form a small bag
ca. 1.5 x 5 cm). The baggie was evacuated and refilled with argon three times,
and then evacuated and heat sealed. The excess baggie was trimmed off with
standard scissors and then reweighed. The sample weight was found by
subtracting the weight of an equal size piece (typically 4.5 x 0.5 cm) of ziplog
bag from the sealed and trimmed baggie weight. The sample was placed in a
normal drinking straw (origin not known), and its position was fixed securely with
white thread. The sample straw was attached to the SQUID sample rod and
centered according to the length of the sample from the top of the rod. It was
then placed in the air-lock on the instrument. The air was evacuated and
replaced with helium 3 times before the sample was lowered into the
experimental chamber.

The sample was positioned in a 200 G external magnetic field according
to the centering scheme build into the machine. Magnetic susceptibility
measurements were conducted using a general sequence consisting of field
dependence measurements from -200 G to 50,000 G at 1.8 K followed by

temperature dependence measurements from 1.8 K to‘300 K at 200 G. The data

40

collected were extracted into data files consisting of temperatures in K, external
field strength in gauss, induced magnetic moments in emu, and their standard
deviations. The molecular formulas used are assumed to be the same as found
in the X-ray structures. The Yb 1:1 complex 33 was assumed to have the same
structure as the Gd 1:1 complex 29 (based on thermogravimetric analysis and
expected structural similarities). The data were plotted and fitted using Mathcad

3.0 by Mathsoft Inc., 1991.

3.6. X-ray crystallography

Crystal data for NaaGd(triolate)2 32, Na3Yb(trioIate)2 33, La2(triolate)2 28,
and Gd2(triolate)2 29 are given in Table A1 -A4. Atomic positional and isotropic
thermal parameters can be found in Table A5-A12. Intensity data were collected
on either a Rigaku AFCGS diffractometer or a Siemens/Nicolet NICOLET
diffractometer, with graphite monochromated Mo Kd radiation. Structures were
solved using SHELXLS39 and refined by full-matrix least-squares procedures on
F2 using SHELXL97 ‘°. Data collection and analysis were done with the direct
assistance of Dr. D. Ward.

La2(triolate)2-6DMSO 28: A colorless needle of CaHsoNZOnSsLaz having
the approximate dimensions 0.1 x 0.1 x 0.2 mm was mounted on a glass fiber
with a drop of EXXON “paratone-N” oil. The fiber was placed in a stream of N; at
—100 °C. A total of 5186 reflections (:th, tk, 1:!) were collected in a range 094° <
6 < 22.45° with 5186 unique refections used in the refinement of 631 variables.

Final R = 0.0526, wR2 = 0.1434

41

Gd2(triolate)2-4DMSO 29: A colorless rod of CunNZOwS4Gd2 having the
approximate dimensions 0.1 x 0.1 x 0.4 mm was mounted on a glass fiber with a
drop of oil. The fiber was placed in a stream of N; at —100 °C. A total of 5421
reflections (:th, :tk, :I:/) were collected in a range 4° < 28 < 50° with 5324 having I.
> 0.1 o ( I.) being used in the refinement of 377 variables. Final R = 0.0318, wR2
= 0.0727.

NasGd(triolate)202H20°6CH;OH 32: A colorless needle of
C42H52N2014GdNa3 with the approximate dimensions 0.1 x 0.1 x 0.6 mm was
mounted on a glass fiber with a drop of oil. The fiber was placed in a stream of
N; at —100 °C. A total of 2927 reflections (:th, :tk, 1:!) were collected in a range 4°
< 28 < 40° with 2107 having I. > 0.05 o ( I.) being used in the refinement of 322
variables. Final R = 0.0526, wR2 = 0.1268. It should be noted that the data
crystal was lost midway into the third shell of data collection (40-45 degrees 28).
Because of this (and to maintain a constant resolution in all directions in
reciprocal space) data with 28 greater than 40 degrees either was never
collected or was discarded. This resulted in a data set containing only half the
expected number of reflections for this crystal. This lack of data forced us to
highly constrain our model. Some of the constraints include forcing the phenyl
rings to have all the same C-C distances, the same C-C-C bond angles, and all
carbons lying on the same plane. The hydrogen atoms were also fixed on their
corresponding carbons at idealized positions.

Na;Yb(triolate)2~2H20-SCHaOH 33: A colorless needle of

C41H48N2013YbNa3 with the approximate dimensions 0.07 x 0.1 x 0.2 mm was

42

mounted on a glass fiber with a drop of oil. The fiber was placed in a stream of
N; at -100 °C. A total of 4162 reflections (1h, tk, 1:!) were collected in a range
245° < 8 < 22.37° with 3832 having I. > 0.05 o ( I.) being used in the refinement
of 358 variables. Final R = 00555, W = 01541

As with 32 the data set for 33 was also incomplete as coincidentally the data
crystal was lost at about the same point as in the Gd 2:1 crystal 32. The lack of
data forced us to refine all atoms as isotropic except for Yb1, Na3, and Na4. The
structure was also highly constrained using the same constraints as were used

for the Gd 2:1 32 complex.

43

APPENDIX

44

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NAVENUMBERS

FTIR spectrum of trisodium triolate 27 (KBr pellet).

1700.0

Figure A.4

 

Figure A.5: Drawing of La2(triolate)2-6DMSO 28 showing thermal ellipsoids and
atom labeling scheme. Hydrogens are omitted.

49

. A
,,,/
\l‘)

sm 2 Sll CI2AI
<9 0") N?”
a 5...‘
0m , a.
7’0‘ ’9 ‘ 0(2) C(28)

C(18)

 
   
   
  
  

0l3ll
”.8

C(33,_ 9 C(32)
‘7
ol34l\

Clasl"

Figure A.6: Drawing of Gd2(triolate)2-4DMSO 29 showing thermal ellipsoids and
atom labeling scheme. Hydrogens are omitted.

50

fluff, 0‘3,

(«7
0(3)
mm \‘"o
O NO", (: Ill\ 0(2)

'-‘ ‘I'

OI4VI’ ¢/“-'

  
 

Figure A.7: Drawing of NaaGd(triolate)2-2H20-6CH30H 32 showing thermal
ellipsoids and atom labeling scheme. Hydrogens are omitted.

51

 

 

 

 

 

 

 

Figure A.8: Drawing of NaaYb(triolate)2-2H20-5CH30H 33 showing thermal
ellipsoids and atom labeling scheme. Hydrogens are omitted.

52

Table A1: Crystallographic data for La2(triolate)2-6DMSO 28

 

Empirical formula
Formula weight
Temperature
Wavelength

Crystal system
Space group

Unit cell dimensions

Volume

Z

Density (calculated)
Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected I unique
Completeness to theta = 22.45
Refinement method

Data / restraints I parameters
Goodness-of-fit on F2

Final R indices [l>20(l)]

R indices (all data)

Largest diff. peak and hole

C48H80L32N201236

1327.16

173(3) K

0.70926 A

triclinic

P-1 (# 2)

a = 13.401(5) A

b = 21.930(12) A

c = 10.193(5) A

a = 100.28(4) deg.

B = 112.28(3) deg.

y = 8337(4) deg.

2724(2) A3

2

1.618 Mg/m’

1.837 mm"

1336

0.1x 0.1x 0.2 mm

0.94 to 22.45 deg.
Oshs12,-23sk523,-105Is10
5186 I 5186 [R(int) = 0.0000]
72.80%

F ull-matrix least-squares on F2
5186 I 144 I631

1.178

R1 = 0.0526, sz = 0.1434
R: 0.1101, sz = 0.1854
0.980 and -1.034 9A"

53

Table A.2:Crystallographic data for Gd2(triolate)2-4DMSO 29

 

Empirical formula
Formula weight
Temperature
Wavelength

Crystal system
Space group

Unit cell dimensions

Volume

2

Density (calculated)
Absorption coefficient

F(000)

Crystal size

Theta range for data collection
lndexranges

Reflections collected I unique
Completeness to theta =27.61
Refinement method

Data I restraints I parameters
Goodness-of-fit on F2

Final R indices [l>20(l)]

R indices (all data)

Extinction coefficient

Largest diff. peak and hole

C22H24GdN0582

603.79

293(2) K

0.71069 A

triclinic

P-1 (# 2)

a = 10.314(2) A

b = 10.360(2) A

c = 11.404(2) A

a = 8037(2) deg.

B = 7633(2) deg.

y = 7766(2) deg.

1147.9(4) It3

2

1.747 Mg/m3

3.104 mrn'1

598

01x01x04mm

2.57 to 27.61 deg.
-65hs13, -135ks 13, -14sls 14
5421 I 5324 [R(int) = 0.0427]
99.6%

F ulI-matrix least-squares on F2
5324 I 0 I 377

1.090

R = 0.0318, sz = 0.0727
R1 = 0.0388, sz = 0.0762
0.0034(4)

1.247 and -1.730 e. A'3

54

Table A.3: Crystallographic data for NaaGd(triolate)2-2H20-60H30H 32

 

Empirical formula
Formula weight
Temperature
Wavelength

Crystal system
Space group

Unit cell dimensions

Volume

2

Density (calculated)
Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected / unique
Completeness to theta = 19.97
Refinement method

Data I restraints I parameters
Goodness-of-fit on F2

Final R indices [l>20(l)]

R indices (all data)

Largest diff. peak and hole

C21H26Gd0.50NNa1.5007
517.54

173(3) K

0.71069 A

monoclinic

C2Ic (# 15)

a = 1950(4) A

b = 15.313(11) A

c = 15.266(11) A

or = 90 deg.

B = 90.71(12) deg.

y = 90 deg.

4559(10) A3

8

1.508 Mglm’

1.549 mrn'1

2108

01x01x06mm

2.66 to 19.97 deg.
05h518, 05k514, -145I514
2184 I 2107 [R(int) = 0.0549]
99.80%

Full-matrix least-squares on F2
2107 l 9 I 322

1.123

R. = 0.0526, sz = 0.1268
R1 = 0.0698, ng = 0.1517
1.547 and 2.530 e. A'3

55

Table A4: Crystallographic data for Nang(triolate)2-2H20-5CH30H 33

 

Empirical formula
Formula weight
Temperature
Wavelength

Crystal system
Space group

Unit cell dimensions

Volume

2

Density (calculated)
Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected 1 unique
Completeness to theta = 22.54
Refinement method

Data l restraints I parameters
Goodness-of-fit on F2

Final R indices [l>20(l)]

R indices (all data)

Largest diff. peak and hole

C41H43N2N33013Yb

1018.82

213(5) K

0.71069 A

triclinic

P-1 (# 2)

a = 12.450 A

b = 13.179 A

c = 15.262 A

a = 111.35 deg.

B = 90.16 deg.

y = 110.68 deg.

2157.1 A3

2

1.589 Mg/m3

2.253 mm"

1030

0.07 x 0.1 x 0.2 mm

2.45 to 22.54 deg.

-25h57, ~145k513, -165I516
4162 I 3832 [R(int) = 0.0542]
67.30%

Full-matrix least-squares on F2
3832 I 1519 I 358

1.115

R1 = 0.0655, wR2 = 0.1541
R1 = 0.1040,sz = 0.1906
2.215 and -1549 e. A”3

56

Table A.5: Atomic coordinates ( x 10"), equivalent isotropic displacement

parameters (A2 x 103), and occupancies for La2(triolate)2-60MSO 28

 

 

Atom x y z U(eq) 0cc.
La(1) 2217(1) 3188(1) 8073(1) 21(1) 1
La(2) 1651(1) 1580(1) 5471(1) 19(1) 1
S(1 ) 2260(5) 5002(2) 9054(6) 36(2) 1
S(2A) -302(6) 4222(3) 7223(9) 32(3) 074(2)
S(28) -850(30) 3792(15) 7310(30) 73(13) 026(2)
8(3) 3744(4) 2407(2) 5179(6) 30(1 ) 1
8(4) 2621 (5) 174(3) 3629(6) 38(2) 1
8(5) 1460(4) 186(2) 6562(5) 26(1 ) 1
8(6) 801 (4) 1853(2) 8697(6) 26(1 ) 1
0(1 ) 1914(1 1 ) 4373(6) 8982(14) 36(4) 1
0(2) 227(1 1 ) 3564(7) 7264(17) 48(4) 1
0(3) 3001 (1 1 ) 1867(6) 4489(14) 35(4) 1
0(4) 2844(1 1) 570(6) 5062(13) 29(3) 1
0(5) 1924(1 1) 830(6) 7260(13) 29(3) 1
0(6) 1 197(10) 2173(6) 7782(13) 25(3) 1
0(12) 2610(11) 3197(6) 10562(13) 25(3) 1
0(22) 3406(1 1) 3732(5) 7534(13) 23(3) 1
0(32) 3243(10) 2157(5) 7624(13) 22(3) 1
0(42) 1 109(1 1) 1252(6) 2940(14) 26(3) 1
0(52) 1414(10) 2720(5) 5567(13) 20(3) 1
0(62) —83(1 1) 1185(6) 5061 (13) 26(3) 1
N(1 ) 4405(13) 3058(7) 9774(16) 24(4) 1
N(2) -356(12) 2108(7) 3549(15) 17(4) 1
C(18) 2205(17) 5074(10) 7310(20) 38(6) 1
C(1 A) 3675(17) 5013(9) 9910(20) 36(6) 1
C(28) -1520(30) 4090(15) 5760(40) 105(12) 1
C(2A) -730(30) 4338(17) 8670(30) 103(12) 1
C(38) 5028(16) 2048(10) 61 10(20) 41 (6) 1
C(3A) 4020(20) 2605(12) 3730(20) 57(8) 1
C(48) 3246(19) 497(1 1 ) 2670(20) 48(7) 1
C(4A) 3535(17) -487(10) 4030(20) 43(6) 1
C(58) 51 1(19) 109(9) 7290(20) 39(6) 1
C(5A) 2460(18) -330(1 1 ) 7510(20) 48(7) 1
C(68) 1964(18) 1755( 1 1) 10260(20) 42(6) 1
C(6A) 72(19) 2468(1 1 ) 9450(20) 48(7) 1
C(11) 4406(15) 3526(8) 11040(19) 13(5) 1
C(12) 3454(19) 3554(1 1) 1 1330(20) 36(6) 1
C(13) 3409(16) 3981 (8) 12530(20) 22(5) 1
C(14) 4270(20) 4333(13) 13380(30) 60(8) 1

57

Table A.5: continued

 

 

Atom x y z U(eq) Occ.
C(15) 5221 (19) 4279(12) 13120(20) 48(7) 1
C(16) 5282(18) 3817(10) 11940(20) 32(6) 1
C(21 ) 4596(15) 2437(9) 9990(20) 19(5) 1
C(22) 4008(15) 1983(8) 8783(19) 16(5) 1
C(23) 4268(16) 1345(9) 8940(20) 29(5) 1
C(24) 4994(18) 1 158(13) 10160(20) 44(6) 1
C(25) 5504(17) 161 1(9) 11360(20) 32(6) 1
C(26) 5312(16) 2237(10) 1 1240(20) 30(5) 1
C(31 ) 5035(18) 3272(9) 9060(20) 26(5) 1
C(32) 4444(17) 3586(10) 7900(20) 29(5) 1
C(33) 5059(18) 3778(10) 7170(20) 34(6) 1
C(34) 6149(18) 3614(1 1) 7530(20) 37(6) 1
C(35) 6690(20) 3297(9) 8640(20) 31 (6) 1
C(36) 6120(15) 3127(9) 9400(20) 19(5) 1
C(41) -701 (16) 1705(9) 2210(20) 25(5) 1
C(42) 156(18) 1263(8) 1970(20) 20(5) 1
C(43) -160(18) 901 (9) 610(20) 24(5) 1
C(44) -1 188(18) 893(9) -360(20) 29(5) 1
C(45) -1993(19) 1278(10) -70(20) 39(6) 1
C(46) ~1738(16) 1701 (1 1) 1220(20) 33(6) 1
C(51) -138(16) 2726(10) 3410(20) 30(6) 1
C(52) 789(17) 3015(9) 4460(20) 25(5) 1
C(53) 1087(16) 3559(9) 4300(20) 25(5) 1
C(54) 424(19) 3885(10) 3160(20) 41(6) 1
C(55) -490(20) 3600(12) 2130(20) 45(7) 1
C(56) -753(17) 3063(9) 2310(20) 25(5) 1
C(61 ) -1064(16) 2099(9) 4320(20) 25(5) 1
C(62) -867(15) 1622(9) 5105(19) 20(5) 1
C(63) -1512(17) 1561 (10) 5870(20) 37(6) 1
C(64) -2302(19) 2031 (1 1) 5910(30) 47(7) 1
C(65) -2510(17) 2534(10) 5150(20) 37(6) 1
C(66) -1889(15) 2573(9) 4360(20) 20(5) 1
H(1 B1 ) 1467 5075 6656 50 1
H(1 82) 2608 4731 6983 50 1
H(183) 2510 5455 7346 50 1
H( 1 A1 ) 3874 4976 10906 47 1
H(1 A2) 3916 5396 9836 47 1
H(1 A3) 4007 4671 9465 47 1
H(2B1) -1200(110) 3800(110) 5190(160) 136 074(2)
H(282) -1660(150) 4510(40) 5600(200) 136 074(2)
H(283) -1870(120) 3930(130) 6300(150) 136 074(2)

58

Table A.5: continued

 

 

Atom x y z U(eq) Occ.
H(284) -1 100(300) 3900(300) 5200(300) 136 026(2)
H(285) -1400(500) 4520(40) 6140(190) 136 026(2)
H(286) -2220(140) 3900(300) 5500(400) 1 36 026(2)
H(2A1 ) -30(80) 4250(140) 9370(1 10) 133 074(2)
H(2A2) -1240(180) 4020(100) 8290(190) 133 074(2)
H(2A3) -1000(200) 4760(50) 8600(200) 133 074(2)
H(2A4) 0(200) 4200(200) 9300(300) 1 33 026(2)
H(2A5) -1 300(400) 4300(200) 9000(500) '1 33 026(2)
H(2A6) -800(600) 4710(40) 8200(200) 133 026(2)
H(3B1) 5014 1916 6956 53 1
H(382) 5578 2340 6388 53 1
H(3B3) 5182 1695 5501 53 1
H(3A1) 3392 2805 3107 74 1
H(3A2) 4226 2235 3207 74 1
H(3A3) ~ 4606 2882 4107 74 1
H(4B1 ) 2845 869 2353 62 1
H(482) 3259 203 1860 62 1
H(4B3) 3971 594 3290 62 1
H(4A1) 3317 -725 4575 56 1
H(4A2) 4251 -353 4583 56 1
H(4A3) 3526 -740 3157 56 1
H(581) -122 368 6877 50 1
H(582) 808 232 8307 50 1
H(583) 321 -316 7081 50 1
H(5A1 ) 3078 -347 7248 72 1
H(5A2) 21 83 -736 7293 72 1
H(5A3) 2665 -1 89 8524 72 1
H(681 ) 2449 1438 10023 54 1
H(682) 1747 1635 10974 54 1
H(683) 2320 2138 10636 54 1
H(6A1 ) -598 2572 8720 63 1
H(6A2) 498 2826 9835 63 1
H(6A3) -72 2332 10206 63 1
H(1 3) 2787 4023 12745 10(40) 1
H(14) 4210 4616 14143 80(90) 1
H(1 5) 5794 4527 1 3682 20(50) 1
H(16) 5936 3725 11803 0(40) 1
H(23) 3926 1045 81 81 0(40) 1
H(24) 5158 737 10221 180(190) 1
H(25) 5967 1487 12221 10(40) 1
H(26) 5670 2528 12014 10(50) 1

59

Table A.5: continued

 

 

Atom x y z U(eq) 0cc.
H(33) 4717 4017 6434 70(90) 1
H(34) 6518 3723 7004 50(70) 1
H(35) 7421 3196 8894 60(90) 1
H(36) 6486 2907 10159 0(40) 1
H(43) 367 652 357 50(70) 1
H(44) -1351 626 -1220 0(40) 1
H(45) -2700 1260 --728 50(70) 1
H(46) -2271 1975 1402 10(50) 1
H(53) 1 733 3722 4952 80(80) 1
H(54) 590 4277 3106 0(40) 1
H (55) -900 3784 1 320 500(600) 1
H(56) -1394 2900 1651 30(70) 1
H(63) -1420 1219 6336 60(80) 1
H(64) -2706 201 1 6468 40(60) 1
H(65) -3056 2834 5168 30(60) 1
H(66) -2001 2906 3865 90(90) 1

 

U(eq) is defined as one third of the trace of the orthogonalized U] tensor.

6O

Table A6: Anisotropic displacement parameters (A2 x 103) for
La2(triolate)2-60MSO 28

 

 

Atom U1 1 022 U33 U23 U13 U12
La(1) 24(1) 15(1) 22(1) 1(1) 9(1) -2(1)
La(2) 24(1) 17(1) 18(1) 0(1) 10(1) -3(1)
S(1) 45(4) 19(3) 50(4) 2(3) 27(3) -1(3)
S(2A) 31(5) 9(5) 52(5) 12(4) 23(4) 5(3)
5(3) 34(3) 23(3) 35(3) -4(3) 19(3) -5(3)
S(4) 39(4) 29(3) 37(4) -5(3) . 10(3) 0(3)
5(5) 38(3) 13(3) 27(3) 1(2) 12(3) -2(2)
5(5) 35(3) 17(3) 32(3) 1(2) 19(3) 5(3)
0(2) 17(8) 41 (10) 70(12) -21(8) 11(8) 1(7)
0(3) 35(9) 39(9) 32(9) -12(7) 17(7) -20(7)
0(4) 43(9) 21(8) 24(8) 4(5) 15(7) 10(7)
0(5) 39(9) 24(8) 22(8) 1(5) 11(7) -3(7)
0(5) 34(9) 25(8) 24(8) 7(5) 19(7) 0(7)
0(12) 34(9) 17(8) 27(8) 1(5) 15(7) -1 (7)
0(22) 29(10) 15(8) 30(8) 5(5) 15(7) -8(7)
0(32) 30(8) 15(8) 19(8) 2(5) 5(7) 0(5)
0(42) 21(9) 37(9) 15(8) -1(5) 7(8) 7(7)
0(52) 27(8) 13(7) 20(8) 8(5) 5(7) -1(5)
0(52) 33(9) 23(8) 25(8) -1(5) 15(7) -2(7)
N(1) 34(11) 25(10) 17(9) 5(8) 17(8) 5(8)
N(2) 24(10) 15(10) 13(9) -5(7) 11(8) -10(8)
C(18) 35(14) 39(14) 45(15) 2(11) 20(12) -7(11)
C(1A) 51(15) 14(12) 39(14) -5(10) 14(12) -8(11)
C(28) 100(30) 80(30) 100(30) 20(20) 0(20) 40(20)
C(2A) 1 10(30) 150(30) 70(20) -10(20) 70(20) 10(20)
C(38) 32(14) 35(14) 53(15) -2(12) 19(12) 4(11)
C(3A) 73(19) 73(19) 45(15) 15(14) 32(14) -37(15)
C(48) 57(17) 50(17) 35(14) 5(12) 30(13) 5(14)
C(4A) 38(15) 31(14) 49(15) -4(11) 9(12) 1(11)
C(58) 73(18) 15(12) 37(14) 5(10) 27(13) -15(12)
C(58) 54(15) 53(15) 28(13) 12(11) 20(12) -21(13)
C(6A) 50(17) 68(18) 40(15) , 19(13) 41(14) 5(14)
C(12) 53(15) 52(15) 11(12) -12(11) 21(12) -24(14)
C(14) 50(20) 90(20) 25(15) -11(15) 21(14) -14(15)
C(15) 35(15) 80(20) 17(13) -5(13) 0(12) -24(15)
C(16) 34(15) 40(14) 19(13) 2(11) 5(11) -3(11)
C(24) 35(15) 55(19) 38(15) 18(13) 14(12) -5(13)
C(25) 33(14) 33(14) 23(13) 14(11) 4(11) -11(11)
C(31) 41(15) 20(12) 22(13) -2(10) 15(12) -13(11)

61

Table A.6: continued

 

 

Atom 01 1 022 033 023 013 012
C(32) 23(15) 40(14) 27(13) 5(11) 7(12) -15(12)
C(33) 35(15) 31 (14) 29(14) -2(11) 5(12) -13(12)
C(34) 30(15) 53(17) 15(13) 4002) 10(12) -15(13)
C(35) 53(18) 14(12) 24(14) -15(10) 19(13) 5(11)
C(35) 10(13) 27(12) 15(11) 5(10) 3(10) 3(10)
C(42) 38(15) 15(12) 9(12) 3(9) 9(11) -10(10)
C(43) 34(15) 11(11) 24(13) -1(10) . 8(12) -8(11)
C(44) 42(15) 15(12) 22(13) -9(10) 7(13) -4(11)
C(45) 35(15) 45(15) 23(14) -14(12) 0(13) -17(13)
C(46) 13(13) 52(15) 35(15) 21(12) 4(11) -4(12)
C(51) 14(13) 55(15) 20(12) 8(11) 5(11) 5(11)
C(52) 32(14) 22(12) 28(13) 8(10) 21(12) 10(11)
C(54) 63(18) 21(14) 55(17) 18(12) 35(15) 14(13)
C(55) 42(15) 59(19) 23(13) 9(13) 10(13) -1(14)
C(51) 30(13) 20(12) 28(12) 0(10) 14(11) -4(10)
C(52) 17(12) 31(13) 10(11) -5(10) 7(10) -2(11)
C(63) 29(14) 30(14) 50(15) 5(12) 28(13) -3(11)
C(65) 35(14) 32(14) 57(15) 5(12) 37(13) 19(12)

 

The anisotropic displacement factor exponent takes the form:

-21t2[h2a*2U11+...+2hka*b*U12]

62

Table A.7: Atomic coordinates ( x 10"), equivalent isotropic displacement

parameters (A2 x 103), and occupancies for Gd2(triolate)2-4DMSO 29

 

 

Atom x y z U(eq) Occ.
Gd(1) 666(1) -247(1) 1488(1) 13(1) 1
S(1) 2683(1) 2277(1) -96(1) 23(1) 1
8(2) 894(1) 1879(1 ) 3543(1) 26(1) 1
0(1) 1432(3) 1784(3) 671 (3) 19(1) 1
0(2) 178(4) 887(4) 3221(3) 26(1) 1
0(11) -718(3) -1494(3) 2769(3) 17(1) 1
0(21) 2868(3) -960(3) 1761(3) 19(1) 1
0(31) 1108(3) -813(3) -485(3) 14(1) 1
N(1) 1529(4) -281 1(4) 1366(3) 15(1) 1
C(1A) 3799(6) 2103(6) 931 (6) 33(1 ) 1
C(18) 3591(6) 947(6) -943(5) 29(1) 1
C(2A) -304(7) 2694(6) 4697(5) 34(1 ) 1
C(28) 2032(7) 882(8) 4442(6) 42(2) 1
C(1 1 ) 308(4) -3389(4) 1740(4) 16(1 ) 1
C(12) -785(4) -2679(4) 2523(4) 16(1 ) 1
C(13) -1924(5) -3279(5) 3014(4) 20(1) 1
C(14) -1 996(5) -4504(5) 2708(4) 23(1) 1
C(15) -937(5) -5162(5) 1898(4) 22(1) 1
C(16) 217(5) -4605(4) 1415(4) 18(1) 1
C(21 ) 2374(4) -3150(4) 2276(4) 15(1 ) 1
C(22) 3051(4) -2145(4) 2407(4) 17( 1) 1
C(23) 3879(5) -2464(5) 3278(4) 21 (1 ) 1
C(24) 3997(5) -3689(5) 3995(4) 23(1 ) 1
C(25) 3305(5) -4643(5) 3868(4) 22(1 ) 1
C(26) 2490(5) -4377(5) 2997(4) 19(1 ) 1
C(31 ) 2295(4) -2943(4) 133(4) 14(1 ) 1
C(32) 2035(4) -1884(4) -772(4) 15(1) 1
C(33) 2779(5) -1993(5) -1 964(4) 19(1) 1
C(34) 3740(5) -31 15(5) -2238(4) 20(1) 1
C(35) 3998(5) -4163(5) -1340(4) 20(1 ) 1
C(36) 3278(4) -4066(4) -160(4) 18(1 ) 1
H(1 83) 4540(80) 900(70) -1380(70) 50(20) 1
H(1 A1 ) 3940(60) 1 150(70) 1420(60) 41 (17) 1
H(1A2) 3390(60) 2740(60) 1490(50) 26(14) 1
H(1B1) 3210(40) 710(40) -1570(40) 2(10) 1
H(182) 3650(50) 160(50) -330(50) 14(12) 1
H(1A3) 4620(60) 2300(60) 480(60) 34(16) 1
H(281 ) 2680(80) 340(80) 3900(70) 60(20) 1
H(2A3) -530(80) 2050(80) 5310(70) 60(20) 1

63

Table A.7: continued

 

 

Atom x y z U(eq) Occ.
H(2A1) 160(80) 3210(80) 5010(70) 60(20) 1
H(2A2) -1030(80) 3140(70) 4350(70) 60(20) 1
H(282) 2460(80) 1490(80) 4740(70) 60(20) 1
H(283) 1600(80) 380(70) 5100(70) 50(20) 1
H(13) -2710(50) —2820(50) 3530(50) 21 (13) 1
H(14) -2850(50) -4830(50) 3070(50) 19(13) 1
H(15) -980(50) -5970(60) 1680(50) 23(14) 1
H(16) 970(60) -5070(50) 850(50) 24(14) 1
H(23) 4320(60) -1840(60) 3410(50) 28(15) 1
H(24) 4550(50) -3850(50) 4580(50) 22(13) 1
H(25) 3430(60) -5440(60) 4340(50) 26(14) 1
H(26) 2030(60) -4980(60) 2880(50) 26(14) 1
H(33) 2640(50) -1280(50) -2560(40) 12(1 1) 1
H(34) 4330(50) -3150(50) -31 10(50) 21 (13) 1
H(35) 4700(50) -5030(50) -1530(50) 19(13) 1
H(36) 3440(50) -4780(50) 520(40) 10(11) 1

 

U(eq) is defined as one third of the trace of the orthogonalized U.) tensor.

64

Table A.8: Anisotropic displacement parameters (A2 x 103) for
Gd2(triolate)2-4DMSO 29

 

 

Atom 01 1 022 033 023 013 012
Gd(1) 14(1) 14(1) 11(1) -2(1) 5(1) -1(1)
5(1) 25(1) 19(1) 24(1) 2(1) 5(1) -7(1)
5(2) 32(1) 29(1) 19(1) -10(1) 5(1) -9(1)
0(1) 22(2) 13(1) 22(2) 1(1) -3(1) -7(1)
0(2) 28(2) 35(2) 20(2) -12(1) -4(1) 42(2)
0(11) 21(2) 14(1) 12(1) 4(1) . 2(1) -10(1)
0(21) 18(2) 15(2) 24(2) 3(1) -12(1) -1(1)
0(31) 15(1) 10(1) 15(1) -3(1) 5(1) 3(1)
N(1) 14(2) 19(2) 10(2) 1(1) -4(1) 0(1)
C(1A) 25(3) 35(3) 40(3) -4(3) 43(2) -10(2)
C(18) 25(3) 35(3) 25(3) -7(2) 2(2) 5(2)
C(2A) 44(3) 34(3) 22(3) -15(2) 5(2) 10(3)
C(28) 35(3) 59(4) 32(3) -20(3) -14(3) 5(3)
C(11) 17(2) 18(2) 12(2) 2(2) 5(2) 5(2)
C(12) 18(2) 18(2) 11(2) 2(2) «1(2) 5(2)
C(13) 21(2) 25(2) 15(2) 5(2) 5(2) 5(2)
C(14) 24(2) 29(2) 18(2) -2(2) 5(2) -11(2)
C(15) 29(2) 23(2) 20(2) 5(2) -10(2) -11(2)
C(15) 19(2) 18(2) 17(2) -1 (2) -7(2) 5(2)
C(21) 11(2) 22(2) 12(2) -2(2) 5(2) 1(2)
C(22) 17(2) 15(2) 18(2) -4(2) -7(2) 0(2)
C(23) 20(2) 25(2) 19(2) -3(2) -9(2) -1(2)
C(24) 21(2) 29(2) 18(2) -3(2) -11(2) 4(2)
C(25) 23(2) 23(2) 15(2) 3(2) -7(2) 2(2)
C(26) 15(2) 20(2) 19(2) -2(2) 5(2) -1(2)
C(31) 15(2) 12(2) 15(2) 5(2) 5(2) -1(2)
C(32) 15(2) 15(2) 18(2) -4(2) -8(2) -3(2)
C(33) 21(2) 22(2) 13(2) 0(2) 5(2) -4(2)
C(34) 20(2) 23(2) 19(2) -9(2) -3(2) 5(2)
C(35) 15(2) 21(2) 24(2) -9(2) 5(2) 1(2)
C(35) 15(2) 17(2) 20(2) -3(2) 5(2) 1(2)

 

The anisotropic displacement factor exponent takes the form:

-2n°[h°a*°011+...+2hka*b*012]

65

Table A.9: Atomic coordinates ( x 10‘), equivalent Isotropic displacement

parameters (A2 x 103), and occupancies for NaaGd(triolate)2-2H20-60H30H 32

 

 

Atom x y z U(eq) 0cc.
Gd(1) 0 528(1) 2500 23(1) 1
Na(1) 11(3) 2170(3) 753(3) 38(1) 1
Na(2) 0 0 0 76(3) 1
0( 1) 4453(8) 737(8) 6744(9) 100(5) 1
C(1 A) 4150(30) -90(40) 6990(40) 84(19) 057(9)
C(1 B) 3880(40) 230(50) 6730(40) 80(20) 043(9)
0(2) 732(5) 2961(5) 1883(6) 44(2) 1
C(2) 1407(8) 31 81 (10) 1618(10) 56(4) 1
0(3) -151(6) 3561(6) 213(7) 71(3) 1
C(3) -524(1 1) 3852(1 1) -523(14) 92(7) 1
0(4W) -435(7) 1427(6) -525(7) 36(3) 1
0(1 1) 406(4) -643(4) 3359(4) 21 (2) 1
0(21 ) 475(4) 787(5) 1 106(5) 26(2) 1
0(31) 717(4) 1681(5) 3056(5) 30(2) 1
N(1 ) 1345(4) 237(6) 2400(6) 18(2) 1
C(11) 1384(6) -715(8) 2418(7) 25(3) 1
C(12) 873(6) -1 1 18(8) 2928(8) 29(3) 1
C(13) 869(7) -2037(7) 2956(9) 33(3) 1
C(14) 1345(7) -2507(8) 2524(8) 36(3) 1
C(15) 1836(7) -2110(8) 2010(8) 36(3) 1
C(16) 1851(6) -1207(8) 1966(7) 29(3) 1
C(21) 1627(5) 657(7) 1637(7) 20(3) 1
C(22) 1147(7) 907(7) 971 (7) 24(3) 1
C(23) 1402(6) 1284(7) 225(7) 24(3) 1
C(24) 2090(7) 1459(8) 143(8) 33(3) 1
C(25) 2547(7) 1259(8) 792(9) 35(3) 1
C(26) 2313(7) 851(8) 1542(8) 31(3) 1
C(31) 1612(5) 635(7) 3224(7) 18(3) 1
C(32) 1302(6) 1408(8) 3487(7) 26(3) 1
C(33) 1574(7) 1866(9) 4188(9) 33(3) 1
C(34) 2107(9) 1496(12) 4644(13) 48(6) 1
C(35) 2405(9) 728(10) 4422(9) 41(4) 1
C(36) 2147(8) 307(10) 3692(10) 36(4) 1
H(1 0) 4540(70) 840(100) 7370(1 10) 70(50) 1
H(1 A1 ) 4470(80) -540(1 10) 7350(100) 10(40) 057(9)
H(1A2) 3970(90) -60(1 10) 7360(120) 0(60) 057(9)
H(1A3) 4080(120) -420(150) 6300(160) 70(70) 057(9)
H(20) 729 2510 2304 100(60) 1
H(2A) 1668 2657 1533 300(200) 1

66

Table A.9: continued

 

 

Atom x y z U(eq) Occ.
H(28) 1624 3532 2063 50(40) 1
H(20) 1 385 3504 1079 1 00(70) 1
H(3A) -400(100) 4380(1 10) -810(130) 230(90) 1
H(3B) -1000(80) 3980(160) -480(110) 230(90) 1
H(SC) -560(120) 3490(120) -1030(110) 230(90) 1
H(4WA) -170(50) 1 360(80) -770(70) 0(40) 1
H(4WB) -810(80) 1660(110) -1000(110) 90(60) 1
H(1 3) 535 -2325 3276 0(20) 1
H(14) 1342 -3113 2573 20(30) 1
H(15) 2150 -2443 1701 10(30) 1
H(16) 2179 -931 1627 20(30) 1
H(23) 1 103 1424 -234 30(30) 1
H(24) 2246 1720 -367 30(30) 1
H(25) 3009 1393 733 0(20) 1
H(26) 2623 707 1987 50(40) 1
H(33) 1360(70) 2490(1 10) 4240(90) 70(50) 1
H(34) 2220(50) 1750(70) 4980(70) 0(40) 1
H(35) 2790(60) 470(80) 4650(80) 30(40) 1
H(36) 2370(50) -1 10(70) 3530(60) 0(30) 1

 

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

67

Table A.10: Anisotropic displacement parameters (A2 x 103) for

NaaGd(triolate)2-2H20-6CH30H 32

 

 

Atom 011 022 033 023 013 012
Gd(1) 41(1) 11(1) 17(1) 0 3(1) 0
Na(1) 51(3) 19(3) 34(3) 5(2) 1(2) 0(2)
Na(2) 143(9) 19(4) 53(5) -9(4) 59(5) 3(5)
0(1) 158(14) 71(9) 70(9) 5(7) 9(9) 55(9)
0(2) 55(5) 24(5) 52(5) 13(5) 0(5) 5(5)
C(2) 79(12) 38(9) 51(10) -7(8) - 19(9) -31(9)
0(3) 123(10) 34(5) 57(7) 18(5) -15(7) 15(5)
C(3) 125(17) 55(12) 93(15) 43(11) -33(14) 5(11)
0(4W) 45(7) 29(5) 33(5) -10(5) 5(5) 14(5)
0(11) 45(5) 13(4) 5(4) -2(3) 5(4) 5(4)
0(21) 33(5) 23(5) 22(4) 2(4) 0(4) -8(4)
0(31) 50(5) 13(4) 25(5) 5(4) 11(4) 5(4)
C(13) 41(8) 8(7) 49(9) 5(5) 7(7) 4(7)
C(14) 57(10) 5(7) 35(8) 7(5) 0(8) 9(7)
C(15) 53(10) 19(8) 25(8) -3(5) 3(7) 18(7)
C(16) 45(8) 30(9) 10(5) 3(5) 5(5) 9(7)
C(22) 47(9) 12(5) 12(7) -7(5) -2(5) -3(5)
C(23) 45(9) 13(7) 12(7) 3(5) 0(5) -4(5)
C(24) 47(10) 18(7) 33(8) 11(5) 3(8) -1 1(5)
C(25) 32(8) 31(8) 40(9) -1(7) 10(7) 5(7)
C(26) 49(9) 25(7) 20(7) 0(5) 0(7) 2(5)
C(32) 34(8) 28(8) 15(7) 13(5) 2(5) 5(5)
C(33) 42(9) 25(8) 32(8) -10(7) 1(7) 5(7)
C(34) 59(14) 45(14) 31(10) 4000) 10(10) -40(12)
C(35) 57(11) 25(10) 30(9) 2(8) 1(8) -8(9)
C(36) 52(9) 11(8) 45(10) -10(7) -3(8) 3(8)

 

The anisotropic displacement factor exponent takes the form:

-2n°[h2a*°011+...+2hka*b*012)

68

Table A.11: Atomic coordinates ( x 10‘), equivalent isotropic displacement

parameters (A2 x 103), and occupancies for Na;Yb(triolate)2-2H20-50H30H 33

 

 

Atom x y z U(eq) 0cc.
Yb(1) 632(1) 496(1) 2641(1) 16(1) 1
Na(1 ) 0 0 0 48(3) 1
Na(2) 0 0 5000 59(3) 1
Na(3) 2548(6) 2165(5) 1449(4) 29(2) 1
Na(4) 2593(6) 2146(5) 4907(4) 29(2) 1
0(1 W) 2023(6) 833(7) 5790(5) 32(3) 1
0(2W) 1335(10) 1948(5) 130(3) 24(3) 1
0(3) 4029(9) 3789(9) 1398(6) 52(4) 1
C(3) 4210(20) 4404(19) 792(15) 84(8) 1
0(4) 4025(7) 21 18(7) 2494(6) 28(3) 1
0(4) 4733(16) 1476(14) 2142(12) 45(5) 1
0(5) 2943(9) 3688(8) 4381(5) 41(3) 1
C(5) 3210(30) 4899(13) 4635(18) 89(8) 1
0(6) 4235(12) 3308(1 1) 5994(8) 53(4) 1
C(6) 4807(19) 3106(18) 6673(13) 61(6) 1
0(7) 5566(1 1 ) 4381(5) 2969(8) 49(3) 1
C(7) 6675(17) 4360(20) 2822(16) 75(7) 1
N(1) -760(9) 1680(7) 3102(5) 14(3) 1
C(1 1) -431(7) 2439(10) 2573(9) 19(4) 1
C(12) 768(10) 2863(10) 2494(9) 22(4) 1
0(12) 1475(7) 2424(7) 2753(6) 20(2) 1
0(13) 1 190(1 1) 3738(9) 2113(8) 20(4) 1
C(14) 377(10) 4067(8) 1746(9) 16(3) 1
C(15) -788(10) 3576(9) 1761 (10) 24(4) 1
C(16) -1189(9) 2759(10) 2186(9) 17(3) 1
C(21 ) -498(10) 2392(9) 4120(6) 22(4) 1
C(22) 210(12) 2126(9) 4658(8) 16(3) 1
0(22) 612(9) 1276(6) 4241(5) 15(2) 1
C(23) 494(10) 2802(9) 5647(6) 21(4) 1
C(24) 1 17(14) 3700(1 1 ) 6070(6) 30(4) 1
C(25) -566(14) 3970(10) 5533(8) 26(4) 1
C(26) -847(13) 3321 (12) 4563(9) 26(4) 1
C(31) -1910(9) 745(9) 2781(7) 20(4) 1
C(32) -1960(9) -242(9) 1949(8) 15(3) 1
0(32) -1001(7) -238(7) 1556(6) 17(2) 1
C(33) -3038(7) -1 167(9) 1554(9) 26(4) 1
C(34) -3994(10) -1 157(9) 2005(9) 25(4) 1
C(35) -3928(12) -213(10) 2836(9) 28(4) 1
C( 36) -2895(13) 737(9) 3206(9) 26(4) 1

69

Table A.1 1: continued

 

 

Atom x y z U(eq) Occ.
N(2) 1272(8) -1 335(8) 1990(6) 14(3) 1
C(41) 1985(10) -1226(9) 1250(8) 21(4) 1
C(42) 1938(1 1) -402(10) 857(9) 20(4) 1
0(42) 1297(8) 241(7) 1205(6) 16(2) 1
C(43) 2627(10) -263(10) 162(8) 30(4) 1
C(44) 3300(1 1) -923(10) -181 (10) 36(4) 1
C(45) 3365(13) -1686(1 1 ) 224(10) 39(5) 1
C(46) 2684(15) -1863(14) 91 1 (10) 33(4) 1
C(51) 1976(13) -1 205(6) 2817(7) 11(3) 1
C(52) 2668(13) -21(8) 3395(8) 15(3) 1
0(52) 2507(9) 870(6) 3266(6) 16(2) 1
C(53) 3447(13) 164(9) 4152(8) 27(4) 1
C(54) 3465(14) -781 (10) 4345(8) 30(4) 1
C(55) 2751 (14) -1925(9) 3777(9) 33(4) 1
C(56) 2000(14) -2130(8) 3000(9) 25(4) 1
C(61) 159(9) -2328(8) 1682(7) 15(3) 1
C(62) -696(12) -2114(8) 2252(7) 17(3) 1
0(62) -452(8) -1085(6) 2986(5) 14(2) 1
C(63) -1771(9) -3034(7) 2007(9) 25(4) 1
C(64) -2001(9) -4096(9) 1237(9) 23(4) 1
C(65) -1 191 (12) -4237(10) 652(10) 31(4) 1
C(66) -92(13) -3359(1 1) 897(9) 24(4) 1
H(10) 4540(70) 840(100) 7370(1 10) 70(50) 1
H(1 A1 ) 4470(80) -540(1 10) 7350(100) 10(40) 057(9)
H(1A2) 3970(90) -60(1 10) 7360(120) 0(60) 057(9)
H(1A3) 4080(120) -420(150) 6300(160) 70(70) 057(9)
H(20) 729 2510 2304 100(60) 1
H(2A) 1668 2657 1533 300(200) 1
H(28) 1624 3532 2063 50(40) 1
H(20) 1385 3504 1079 100(70) 1
H(3A) -400(100) 4380(1 10) -810(130) 230(90) 1
H(38) -1000(80) 3980(160) -480(1 10) 230(90) 1
H(3C) -560(120) 3490(120) -1030(1 10) 230(90) 1
H(4WA) -170(50) 1360(80) -770(70) 0(40) 1
H(4W8) -810(80) 1660( 1 10) -1000(1 10) 90(60) 1
H(13) 535 -2325 3276 0(20) 1
H(14) 1342 -31 13 2573 20(30) 1
H(15) 2150 -2443 1701 10(30) 1
H(16) 2179 -931 1627 20(30) 1
H(23) 1 103 1424 234 30(30) 1
H(24) 2246 1 720 -367 30(30) 1

7O

Table A.1 1: continued

 

 

Atom x y z U(eq) Occ.
H(25) 3009 1 393 733 0(20) 1
H(26) 2623 707 1 987 50(40) 1
H(33) 1 360(70) 2490(1 10) 4240(90) 70(50) 1
H(34) 2220(50) 1750(70) 4980(70) 0(40) 1
H(35) 2790(60) 470(80) 4650(80) 30(40) 1
H(36) 2370(50) -1 10(70) 3530(60) 0(30) 1

 

U(eq) is defined as one third of the trace of the orthogonalized U),- tensor.

 

Table A.12: Anisotropic displacement parameters (A2 x 103) for
Na3Yb(trio|ate)2-2H20-5CH30H 33

 

 

Atom 011 022 033 023 013 012
Yb(1) 19(1) 21(1) 10(1) 11(1) 1(1) 7(1)
Na(3) 30(7) 34(3) 22(3) 17(3) -1(3) 4(3)
Na(4) 25(7) 32(3) 27(3) 15(3) 4(3) 3(3)

 

The anisotropic displacement factor exponent takes the form:
27: [1125:2011 +. ..+2hka* 5*012)

72

 

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