ABSTRACT
PREPARATION AND CHARACTERIZATION OF TRANSITION METAL

COMPLEXES OF SEVERAL S-SUBSTITUTED TETRAZOLES

\
by Paul Labine
In this investigation, cobalt (II), cepper (II), zinc

(II) and chromium (III) ions were caused to react in aqueous
solution with the sodium salts of 5-O-chlorophenyltetrazole,
5-p-chlor0phenyltetrazole, S-p—methoxyphenyltatrazole, 5-p-
chlorobenzyltetrazole, and 5-phenyltetrazole. The divalent
ions generally formed complexes of the type MT .nH 0. However,

2 2
nickel (II) ions formed MT -h 0 complexes. With copper (II)

1.8 2 ‘

ions, two of the tetrazoles formed M(T)(Oh) complexes. The
chromium (III) ions formed MTZOH-nhzo complexes. No complexes
could be obtained for iron (II), iron (III), or manganese (II).

The complexes were generally insoluble in acetone, nitro-
methane, 1,4 dioxane, methylenechloride, benzene, acetonitrile
and methanol. A few of the complexes were insoluble in dime-
thylsulfoxide, N,N-dimethylformamide, and pyridine.

The complexes were usually decomposed by treating the
solids with aqua regia. The c0pper (II) complexes could also
be decomposed with concentrated ammonia but the complexes

could be reformed by neutralizing the ammonia with hydrochloric

acid.

Paul Labine

A comparison of the infrared spectra of the complexes
with the spectra of the tetrazoles and their respective
sodium salts indicates that the tetrazoles coordinate as the
anion. That is, the l—nitrogen on the tetrazole ring is not
protonated during complexation.

In most cases, the metal-nitrogen stretching hands arise,
on complexation, from the splitting of ligand hands into two
new bands. Very few of the hands in the 130-320 cm.1 re~
pion could be assigned to metal-nitrogen stretching bands
due to the presence of broad bands which could not he re-
solved hy usinp thicker mulls or by increasing the attenuation.
It was therefore impossible to compare the tetrazolcs in
terms of the respective copper-nitrogen stretching frequencies
might have been sufficient to list the tetrazoles in the order
of increasing ligand strength.

The hand positions in the electronic absorption spectra,
could he utilized to list the ligands in the order of increasiny
ligand strength. The electronic absorption spectra of the
solid nickel (II), cobalt (II), and chromium (III) complexes
indicate octahedral symmetry. The spectra of the copper (ll)
complexes indicate tetragonal distortion.

The calculated magnetic moments indicate that most of the
complexes are of the high-spin type. however, a few of the

capper (II) complexes have subnormal magnetic moments which may

indicate metal-metal bonding.

Paul Labine

The esr spectra of the copper (II) complexes, diluted
with zinc (II) ions, indicate tetragonal distortion due to
differences of approximately 0.15 between g!l and gl for
several of the copper (II) complexes.

The esr parameters for the chromium (III) complexes
were quite similar to those obtained for octahedral complexes
of chromium (III).

The esr spectra of the nickel (II) and cobalt (II)
complexes were generally quite complex and poorly resolved.
Only his (5-0-chlorophenyltetrazolato)cobalc(II) monohydrate
gave an esr signal that could easily be interpreted. The
gave value of this complex increased with a decrease in

temperature. This unusual behavior may be due to changes in

the structure of the complex with changes in temperature.

PREPARATION AND CHARACTERIZATION
OF TRANSITION METAL COMPLEXES OF

SEVERAL 5-SUBSTITLTED TETRAZOLES

hy‘\

Paul Labine

A THESIS

Submitted to

Michigan State University

in partial fulfillment of the requirements

for the degree of
DOCTOR OF PHILOSOPHY

Department of Chemistry
1970

MI KNUNLEDCM MT

The author gratefully acknowledges Carl U. Bruhaker, Jr.
for his guidance, patience and encouragement. The author
wishes to acknowledgment his wife, Joyce, whose understanding,
assistance and reassurance made this dissertation possible.

Appreciation is extended to Dr. C. Van hall, Dow Chemical
Company, for permission to use the Beckman Mode] UK-2 with
reflectance attachment.

Appreciation is also extended to my fellow graduate
students for their helpful suggestions.

Financial assistance from the National Institutes of

health is gratefully acknowledged.

Tabl e of

Contents

1. historical................................
II. Experimental..............................
A. Purity of Chemicals and Solvents.....

B. Preparation of Tetrazoles and Related

(:l‘emicalSOOOO0.0000000000000I.

C. Preparation of Metal Complexes

U. Analytical Methods.

CObaICOOOOCCOOOOCOO
:JiCkel-OOOOOOC. .0...
copper.............

Cllromium.OOOCOOOOOOOOOOOO
and

Carbon, Hydrogen

h. Magnetic Measurements.......

F. Spectrosc0pic Measurements.

Discussion of Results..........

Preparation of Metal Complexes.

Infrared Spectra...............

Electronic Absorption Spectra..

Magnetic

Electron Spin Resonance

Measurements. o o o o o o oo o

Spectra.

liefcrche-QOO00000000000000.000000.00.

iii

Nitrogen.

O O O l
..12
..12

..12

...lS

..22

...22

..23
..23
..2A

..24
0027
..29

..30
..n5
.117
.l?l
.130

Table

1.

II.

IV.

VI.

IX.

List of Tables

page

Solubility of the Cobalt (II) Complexes in
. 0
Various Solvents at 22 ........................34

Solubility of the hickel (II) Complexes in
. . 0 ,-
Various Solvents at 22 ........................3)

Solubility of the Coppgr (II) Complexes in
VEII‘IOUS SOIVCHCS at 22 .ooooooooooooooooooooooo?’(I

Solubility of the Chromium (III) Complexes
in Various Solvents at 22 .....................37

Solubility of the Zinco(II) Complexes in
Various solvents at 22 0......OCOOOQOO0.0.0....38

Infrared Spectra of 5-Phenyltetrazole, Sodium
5-Phenyltetrazolate and Various Complexes of
5-Phenyltetrazole in Nujol and Hexachloro-
butadiene Mulls from 4000 to 167cm 1...........39

Infrared Spectra of 5-Phenyltetrazole and
Sodium S-Phenyltetrazolate with Assignments....44

Infrared Spectra of S—p-Methoxyphenyltetrazole,
Sodium 5-p-Hethoxyphenyltetrazolate and Various
Complexes of S-p-Hethoxyphenyltetrazole in hujol
and Hexachlorobutadiene Mulls from 4000 to

1(7cm- 0.0.0....0......OOOOOOOOOOOOOOOOOI.000004;;

Infrared Spectra of 5-p-Methoxyphenyltetrazole
and Sodium S-p-Methoxyphenyltetrazolate with
ASSiFl‘mcntsOOOOOOOOOOOO0......00....OOOOIOOOOOOSS

Infrared Spectra of S-p-Chlorophenyltetrazole,
Sodium 5-p-Chlorophenyltetrazolate, and Various
Complexes of 5-p-Chlor0phenyltetrazole in Nujol
and Hexaehlorobutadiene Hulls from 4000 to

1(‘7cm‘ 0.00.00.00.0000...}...OOOOOOOOOOOO.0.0.0060

Infrared Spectra of 5-p-Chlorophenyltetrazolc and
Sodium S-p-Chlorophenyltetrazolate with Assign—

Int‘ntSOOOCCOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO.OOOOOO()S

iv

l.ist of Talileti (Ctvutlxuled)
Table page

XI. Infrared Spectra of S-p-Chloropheuyltetrazole and
Sodium S-p-Chlorophenvltetrazolate with Assipn-

n’t‘!1t80000000000OOOOCOOOOOOOOOOOOOOOOOOOOOOOO.OO(’)

XII. Infrared Spectra of S—p-Chlorohenzyltetrazole,
Sodium S—p-Chlorobenzyltetrazole, and Various
Complexes of S-p-Cblorobenzyltetrazole in
Sujol and Hexachlorohutadiene hulls from 4n00

L“)1(‘7cm100......OOOOOOOOOOOCOOCOOOOO.00.0.0.0(I’;

XIIl. Infrared Spectra of 5-p-ChlorohenzvltetraZole
:uml Sodiimn b-p-(Hilorohcuizyltcn:razolc!\Jith
[\SSiv.I‘InentSOOOOOOOOOOOOOOOOOOIOOOOO0.0.00.0000075

XIV. Infrared Spectra of S-o-Chlorophenyltetrazole
Sodium 5-o-Chloropheny]tetrazolate, and Various
Complexes of S-o-Chlorophenyltetrazole in Nujol
and Hexachlorobntadiene Mulls from 4000 to

l()7cm 1.0.0.000000000000OOOOOOOOOOOOOOOOOOOOOO0.?)()

XV. Infrared Spectra of 5-o-Chlorophenyltetrazole
and Sodium S—o-ChlorOphenyltetrazolate with
ASSinnmentSOOOOOOOO0.000.000.00000.000.00one.to"?

XVI. Results of the Normal Coordinate Analysis
Calculation for Sodium Tetrazolate
Honohydratc....................................Ul

XVII. Infrared .‘2 ectrum for Sodium 'l'etrazolate
P

Nonohydrate with AssignmentS................ ..06

thII. Reflectance and Sujol Hull Spectra of Copper(ll)
Perchlorate Hexahydrate and the Copper(ll) Com-
plexes of Various S-Substituted Tetrazoles.....99

XIX. A Comparison of the Reflectance, Nujo] Hull, and
Solution Spectra of C0pper(II) Perchlorate
bexahydrate and the C0pper(II) Complexes of
Various S-Substituted Tetrazoles..............102

XX. reflectance and Hujol Mull Spectra of Cobalt(ll)
Perchlorate Hexahydrate and the Cobalt(II) Com-
plexes of Various S-Substituted Tetrazoles....l04

AAI. A Comparison of the Reflectance, Nujol Hull, and
Solution Spectra of.Coba]t(lI) Perchlorate
Hexahydrate and the Cobalt(II) Complexes of
Various 5-Substituted Tetrazolts..............106

List of Tables (Continued)

Table

XXII.

XXIII.

XXIV.

XXV.

XXVI.

XXVII.

XXVIII.

page

Reflectance and Nujol Mull Spectra of Nickel

(11) Perchlorate Hexahydrate and the Nickel

(II) Complexes of Various 5-Suhstituted
Tetrazoles....................................109

A Comparison of the Reflectance, Nujol Hull,

and Solution Spectra of Nickel Perchlorate
Hexahydrate and the Nickel(II) Complexes of
Various 5—Suhstituted Tetrazoles..............111

Reflectance and Nujol Hull Spectra of Chromium
(III) Perchlorate Hexahydrate and the Chromium
(III) Complexes of Various S-Suhstituted
Tetrazoles....................................ll3

A Comparison of the Reflectance, Nujol Hull,

and Solution Spectra of Chromium(III) Perchlorate
Hexahydrate and the Chromium(III) Complexes of
Various 5-Substituted Tetrazoles..............lIS

Magnetic Moments of the Coba1t(II), Nickel(II),
Chromium(III), and C0pper(II) Canplex of
Various 5-Substituted Tetrazoles..............119

ESR Parameters for the C0pper(II) Complexes of
Various 5-Suhstituted Tetrazoles..............123

FSR Parameters for the Chromium(III) Complexes
of Several S—Suhstituted Tetrazoles...........125

vi

Figure

10.

List of Figures

page

Far Infrared Spectra of S-Phenyltetrazole,
Sodium S-Phenyltetrazolate, and Various
Complexes of 5-Phenyltetrazole..................47

Far Infrared Spectra of S-p-Methoxyphenyltetrazole,
Sodium S-p-Nethoxyphenyltetrazolate, and Various
Complexes of 5-p-Methoxyphenyltetrazole.........59

Far Infrared Spectra of 5-p—Chlorophenyltetrazole,
Sodium 5-p—Chlorophenyltetrazolate and Various
Complexes of S-p-Chlorophenyltetrazole..........68

Far Infrared Spectra of S-p-Chlorobenzyltetrazole,
Sodium S-p-Chlorohenzyltetrazolate and Several
Complexes of 5-p-Chlorobenzyltetrazole..........79

Far Infrared Spectra of S-o-ChlorOphenyltetrazole,
Sodium 5-p-Chloropheny1tetrazolate and Various
Complexes of 5-o-Chlor0pheny1tetrazole..........92

Reflectance Spectra of (A) C0pper(II) Perchlorate
Hexahydrate (B) Bis (5-p-Chlorophenyltetrazolato)
C0pper(II) Monohydrate and (C) Bis(5-o-Chloro-
phenyltetrazolato) C0pper(II) Monohydrate......101

ReerCtance Spectra of (A) Coba1t(II) Perchlorate
Hexahydrate and (B) Bis(5-p-Chlorophenyltetrazolate)
COhalt(II)CCICOOOCOOOOCOICOOCOOOOOCOOOOOOOOOO.0105

Reflectance Spectra of (A) Nickel(II) Perchlorate
Hexahydrate and (B) Nickel Complex of
S-o-Chlorophenyltetrazole......................IIO

Reflectance Spectra of (A) Chromium(III)
Perchlorate Hexahydrate and (B) Hydroxobis
(5-pheny1tetrazolato) Chromium(III)
Tetrahydrate...................................114

ESR Spectra of Bis(5-o-Chlorcphenyltetrazolato)
C0pper(II) Monohydrate at Various Zn:Cu Ratios.126

vii

List of Figures (continued)

Figuire

11.

12.

13.

page

ESR Spectra at Various Temperatures of his
(5-p-Chlorohenzyltetrazolato) C0pper(II)
Trihydrgte Dilutedohy a facgor of 95:10(Zn:Cu)
(A) 30 . (B) -40 to -100 ; (C) -120 ;

(D) -130?oooooo

0......O...00.000.00.00000000000127
A Comparison of the ESR Spectra at ~16O0 of
the C0pper(II) Complexes Diluted by 1000:l
(2n:cu).‘C................CCCOOOO.00...OOOOOOOOIZéB

ESR Spectrum of Bis(5-o-Chlor8phenyltetrazolato)
Cobalt(II) Honohydrate at -40

0.0.0.00000000000129

viii

I. Historical

A. General

Tetrazoles are five membered ring compounds which contain
four nitrogen atoms and one carbon atom. For the structure of

the parent compound, tetrazole, refer to (I).

Thorough reviews (1,2) are available on the preparation
and properties of 5-substituted, 1-substituted, and 1,5-disuh-
stituted tetrazoles. In addition, Popov(3) has prepared an
excellent review of the acidities and complexinp abilities of
various 1,5 disubstituted tetrazoles includinp pentamethvlene-

tetrazole and substituted-pentamethvlenetetrazoles.

B. Acid-Base Properties

The acid-base pronerties of substituted tetrazoles were
investigated as earlv as 1914 hv Olivera-Mandala (A).
Tetrazole and S-suhstituted tetrazoles usuallv have pKa values
of 7 or less. Thus, these tetrazoles can be titrated wifii
strone bases hv usine phenolphthalein as the indicator. The
S-suhstituted tetrazoles can also exhibit basic properties

due to the presence of three other nitrogen atoms. The

hasicities of these S—suhstituted tetrazoles were calculated
from the hydrolysis constant of the resoective hydrochlorides
and appear to he of the same order of magnitude as aniline (l).
Herhst and Hihina (S) and herhst and Wilson (6) determined
potentiometrically the pKa values for S-phenyl and S—alkyl
tetrazoles in water—methanol mixtures. In 1967, Caruso,

Sears, and Popov (7) determined conductometrically the
acidlties of several S-alkvl and S-aryl tetrazoles in l,l,3,3-

tctramethylguanidine. Caruso et al., doubted the usefulness

 

of the pKa values obtained previously in water-methanol
mixtures because changes in liquid junction potential had not
been considered in the previous calculations.

More recently, Charton (8) has calculated the macrosconic
ionization constant KN of several S-substituted tetrazoles.
These macrosconic constants were calculated from microconstants
K1 and K2 which were themselves obtained from the extended

Hammett equation. Since S-substituted tetrazoles exist in two

tautomeric forms, K1 is the ionization constant {or tautomer (I)

and K2 is the ionization constant K”, is then calculated from
k K K .
V, :: 1 2
K + K
I 2

Unlike S-suhstitutcd tetrazoles, l-suhstituted tetrazolvs
do not behave as acids. Stollc SE 31. (9) reported that they

had removed the S-carhon hydrogen from l-phenyltetrazole with

methyl magnesium iodide in ether. Gilbert (10), however, was

unable to remove the 5-carbon hydrogen From l-phenvltetrazole
by their method. In 1967, Barber (11) was successful in re-
moving the S-carbon hydrogen From l-methyl and l-cyclohexvl-
tetrazoles by using n-butyl lithium in anhydrous
tetrahydrofuran. The l-methyltetrazole was converted to
l-methyl-S-tetrazolyl lithium oi tetrahydrofuran, which is
insoluble in tetrahvdrofuran and ether. Although the lithium
salt of l-cvclohexyltetrazole was not isolated as a solid,
l-cvclohexvltetrazole is probably converted to l-cyclohexyl—
5-tetrazolyl lithium. The lithium salts were then caused to
react with dichlorohis(triethylphosphine)nickel(IIJ and gave
bis(l-methvl-S-tetraaolyl)nicke1(II) and bis(1—cyclohexyl-S-
tetrazolyl)nicke1(II).

In a recent publication, Erlich and Popov (12) investi-
gated the acid-base properties 0F cvclopolymethylenetetrazo1es
in formic acid. The unsubstituted cyclopolymethylenctetrazoles
act as fairly strong monoprotic bases in formic acid solution
but show little proton affinity in aqueous solutions. The
length of the hydrocarbon chain does not influence the basic

strength of the tetrazole ring.
C. Characterization of Tetrazoles

Several tetrazoles and azoles have been characterized
by nuclear magnetic resonance spectroscopy (13,14,15) and by

mass spectroscopy (13). In addition, Cuibe and Lucken (16)

reported the 14N pure quadrupole resonance spectra of several

azoles.
D. Coordination Compounds

Since 1892, a large number of metal complexes have been
prepared with S-substituted tetrazoles. Bladin (17) prepared
the first silver complexes of tetrazole and S-substituted
tetrazoles by adding hot silver nitrate to aqueous solutions
of the respective tetrazoles. Herbst and Garbrecht (18)
and Herbst and Mihina (5) prepared silver complexes of other
5-substituted tetrazoles by a similar method.

In 1960, Brubaker (19) prepared two crystalline forms
of bis(S-aminotetrazolato)copper(II). By using spectro-
photometric and pH data, Brubaker calculated the formation
constant for the copper(II) complex formed with S-amino-
tetrazole in aqueous solution. His value of 1012 for the
formation constant indicates that S-aminotetrazole forms a
very stable 2:1 complex with copper(II). Brubaker also
found that there is very little interaction between the
copper(II) ion and 1,5—dimethyltetrazole. This, in addition
to the relatively small formation constant for the 2:]
complex (20) of silver(I) with pentamethylenetetrazole
(hereafter abbreviated PMT), indicates that a replaceable

hydrogen is required to form very stable complexes.

In 1961, Daugherty and Brubaker (21,22) prepared various
bis(5-substituted tetrazolato)copper(II) and nickel(II)
complexes. Methanol solutions of each tetrazole were added
to methanol solutions of capper(II) or nickel(II) salts.
Sulfate and chloride salts induced the rapid precipitation of
solid complexes; whereas, the nitrate salts were ineffective
in inducing precipitation.

The nickel(II) and Copper(II) complexes displayed a few
interesting pronerties. The complexes were insoluble in most
solvents. As a result, they could not be purified by
recrystallization. The complexes usually decomposed below
their melting points. Hence, they could not be purified by
sublimation. The insolubility of these complexes in both
nonpolar znd polar solvents suggests polymer formation.

Jonassen £5 31. (23,24,25) have prepared bis(5-tri-
fluoromethyltetrazolato)iron(II), cobalt(II), nickel(II), and
copper(IT) complexes as well as his(5-chlorotetrazolato)—
iron(II) and bis(5-nitrotetrazolato)iron(IT). The reflectance
spectrum of bis(S-trifluoromethyltetrazolato)iron(II) indicates
that the S-trifluoromethyltetrazolate anion lies between 2,2’.
bipyridine and 1,10-phenanthroline in the spectrochemical
series. The low magnetic moment of 1.1 B.M. observed for
bis(trifluoromethyltetrazolato)iron(II) indicates that "the
paramagnetic state lies close to the spin-paired ground

state." Pyrolysis (26) of the bis(5-trifluoromethyl-

tetrazolato)iron(II), coba1t(II), nickel(II), and copper(II)

complexes yields the components H O, CF3, CN, CN

2 2’ 2’

(CN) for each complex. The residues consisted of CoF

2 3’

NiF FeF The enthalpy of decomposition was calculated

2’ 3'
from differential thermal analyses of the complexes.

In 1967, Beck and fehlhammer (27) prepared bis(5-tri-
fluoromethyltetrazolato)bis(triphenylphosphine)palladium(II)
by reacting bis(triphenylphosphine)palladium(II) azide with
trifluoroacetonitrile in dichloroethane at 00 C. Recently
Beck fig 3l° (28) have prepared several other trans-bis(5-
substitutedtetrazolato)bis(triphenylphosphine) palladium(ll)
by a similar method. Addition of HCl or HN3 in ethanol to
the palladium complexes yields the respective 5-substituted
tetrazoles.

A large number of complexes of l-substituted tetrazoles
are known. In 1910, Olivera-Mandala and Alagna (29) prepared
tetrachlorobis(l-ethyltetrazolato)platinum(IV) by adding an
alcoholic solution of platinum(IV) chloride to an alcoholic
solution containing “Cl and l-ethyltetrazole.

In 1963, Brubaker and Gilbert (30) prepared various
dichloro bis(l—substituted tetrazole)cobalt(II), nicke1(II),
platinum(II) and zinc(II) complexes. Like other tetrazole

complexes, these l-substituted tetrazole complexes cannot be

recrystallized or sublimed. As mentioned previously,

Garber (11) prepared bis(l-methyl-S-tetrazolyl)nickel(II) and
bis(l-cyclohexyl-S-tetrazolyl)nickel(II) by heating'the
respective lithium salts with dichlorobis(triethylphosphine)
nickel(II). These nickel complexes are insoluble in all
common solvents, will decompose when heated, and are seni—
tive to the atmosphere. The reflectance spectra of these
two complexes indicate octahedral symmetry. The magnetic
moments of these nickel complexes indicate that the com-
plexes are high spin.

In 1967, Beck and Fehlhammer (28) prepared tetra-
phenylarsonium tetrakis(l-cyclohexvl-S-tetrazolyl)gold(III)
by reacting tetraphenylarsonium tetrazidogold(III) with
cyclohexylisonitrile in dichloroethane at 0°C. The proton
nmr spectrum in DCCl3 showed three signals at 1-2.4,5.2,8.3
corresponding to the twenty phenyl protons, the four
tertiary hydrogen atoms on the cyclohexylring, and the 40
methylene protons on the cyclohexvl ring.

Tetrazole itself forms metal complexes. Holm and
Donnelly (31) prepared bis(tetrazolato)iron(II), cobalt(II),
nickel(II) and cadmium(II) complexes by adding aqueous
solutions of tetrazole to aqueous solutions of the respect-
ive metal ions. The iron(II) complex is very poorly de-
fined and is easily oxidized by oxygen in the air. Mole

ratio studies indicate that the tetrazolate anion forms

very weak complexes with nickel(II) ions in dimethvlformamide.

In 1967, Carber (11) prepared bis(tetrazolato)cooper(TT)
monohydrate by adding an aqueous tetrazole solution to an
aqueous solution of copper(II) nitrate. The copper(II)
complex decomposes upon heatine and is insoluble in all
common solvents. The reflectance spectrum of the complex
indicates octahedral symmetry. The magnetic moment of the
complex is 1.73 B.M. (l electron value). The esr spectrum of
the undiluted power showed no hyperfine splittings. Garber (11)
was unsuccessful in diluting the copper complex by precipitat-.
ing the c0pper complex as an impurity in bis(tetrazolato)
zinc(II).

(Carber et.al. (11,32) performed a vibrational analysis
of sodium tetrazolate monohydrate. Vibrational assignments
for bis(tetrazolato)copper(II) monohydrate and l-methvl-
tetrazole were made based on their normal coordinate analysis
of sodium tetrazolate monohydrate.

Recently, Washburn and Peterson (33) prepared ferro—
cenyl tetrazole by reacting cyanoferrocene with trimethylazido-
silane and aluminum(III)chloride in refluxing o-chlorobenzene.

1,5 disubstituted tetrazoles and substituted pentamethy-
lenetrazoles form complexes with transition metal ions,
interhalogens, and organic molecules. Interhalogen and

molecular complexes of tetrazoles are reviewed by Popov (3).

Zwikker (34) Rheinboldt (35) and Dister (36) have pre-
pared silver complexes of various substituted pentamethylene-
tetrazoles. Popov and Holm (20) studied the silver complexes
of pentamethylenetetrazole, substituted pentamethylene—
tetrazole, and l-cyclohexyl-S-methyltetrazole in acetonitrile.
They determined potentiometrically that the formation
constants for these complexes were approximately 102. By
using polarographic techniques, they found that pentamethye
lenetetrazole forms extremely weak complexes with cobalt(II),
thalium(I) and cadmium(II) in aqueous solution.

D'Itri and Papov (37,38) prepared anhydrous hexakis
(PMT) manaanese(II), iron(II), cobalt(II), nicke1(II),
copper(II), and zinc(II) complexes. Since the magnetic
moments indicate that the complexes are high spin complexes,
it is not surprising that the infrared spectra of the com-
plexes were almost identical with the infrared Spectrum of
PMT.

Kuska, D'Itri and Popov (39) have obtained electron
spin resonance spectra for Mn(PMT)6(C104)2, Cu(PMT)6(C104)2
and Cu(PMT)6(C104)2. The ear spectrum of Mn(PMT)6(C104)2
dispersed in Zn(PMT)6(C104)2 indicated that the metal
ligand bonds are 91 per cent ionic and that the complexes
are essentially octahedral. Nuclear hyperfine splittings
were resolved in the ear spectra of the undiluted copper(II)

complexes. Both Cu(PMT)6(C104)2 and Cu(PHT)4(CIOA)2

10

exhibit tetragonal symmetry. The copper ligand bonds were
found to be more covalent than the manganese ligand bonds.

Recently, Bowers and Ponov (40) prepared complexes of
the type HII(PMT)1X2 and “11(PMT)2X2 by causing pentamethyl-
enetetrazole to react with first row transition metal chlorides
and bromides. These complexes were insoluble in polar and
nonpolar solvents and have high melting or decomposition
points. Prom magnetic and spectral evidence, it appears that
the metal ions in MII(PMT)X2 complexes are in octanedtal
environments whereas the MII(PMT)2X2 complexes may be tetra-
hedral. The MII(PMT)X2 complexes probably contain haloeen
bridges and are most likely polymeric. The M(PMT)2X2
complexes, on the other hand, are probably monomeric and seem
to have a tetrahedral structure.

Pentamethylenetetrazole (41) was found to form 1:]
complexes with iodine monochloride, iodine monohromide, and
iodine in carbon tetrachloride. The pentamethylenetetrazole-
ICl complex could be obtained as a crystalline solid which
could be purified by recrystallization from chloroform. Two
independent structure determinations of the PMT-ICl complex
(42) showed that PHT acts as a unidentate ligand and that
ICl is bonded to the 4-nitrogen of the tetrazole ring. The
linear ICl molecule is coplanar with the tetrazole ring.

The seven membered ring of PMT is in a chair conformation.

At present, it is uncertain whether the 4-nitrogen is the

11

donor site in all tetrazole complexes.

The crystal structure of dichlorobis(l-methyltetrazole)
zinc(II) complex has also been determined (43). Crystals of
this complex show that the zinc atom is in an approximately
tetrahedral environment and that the zinc atom is ceplanar
with the two tetrazole rings with coordination through the

four position of the tetrazole ring.

II. Experimental

A. Purity of Chemicals and Solvents

Reagent grade chemicals were used throughout this

investigation.
B. Preparation of Tetrazoles and Related Chemicals

5-phenyltetrazole: This compound was prepared according
to the method of Finnegan and Henry (44). Tn a SOOm].3-neck
flask, 28.6g(0.44 mole) of sodium azide, 21.2n(0.40 mole) of
ammonium chloride, 17.0g (0.40 mole) of lithium chloride and
41.2g (0.40 mole) of benzonitrile were suspended in 300ml of
N,N-dimethy1formamide. The mixture was stirred and heated
at IOU-110° for 17 hours. In accordance with Daupherty's
observations (45), the color of the reaction mixture
changed from colorless to orange-brown after a few hours.
After 17 hours, the reaction mixture was allowed to cool to
room temperature. The first batch of crude sodium salt was
separated from the reaction mixture by filtration. The
filtrate was distilled at reduced pressure until 50ml of
filtrate remained in the distillation flask. The second
batch of crude sodium salt, which precipitated durine the
distillation, was collected on a porcelain filter funnel.
Both batches of crude sodium salt were combined and then

dissolved in 200 ml of water. Insoluble materials were re-

12

13
moved by filtration. The filtrate was then acidified to pH=2
to precipitate the water-insoluble 5-phenyltetrazole. The
crude product was collected on a porcelain filter funnel and
thoroughly washed with ice water. The product was finally
recrystallized twice according to the method of Caruso, Popov,
and Sears (7). Crude S-phenyltetrazole was added to 1,2-
dichloroethane and the mixture was brought to boiling. Just
enough methanol was then added to dissolve the tetrazole.
As the solution cooled, needle-like crystals formed. These
crystals were collected by filtration and were then dried to
constant weight in a vacuum dessicator. The melting point of
215° agreed with that previously reported (7).

5-p-chlorobenzyltetrazole: The procedure for the preparation

 

and recrystallization of S-phenyltetrazole was used.
5-p-chloroacetonitrile Eastman Organic Chemicals was used in
place of benzonitrile. The melting point of 162-1630 for the
recrystallized product agreed with that previously reported (7).

5:9-methoxyphenyltetrazole: The same procedure used for the

 

preparation and recrystallization of 5-pheny1tetrazole was
employed. S-anisonitrile was used in place of benzonitrile.
The melting point of 239-2400 for the recrystallized product

agreed with that previously reported (4).

14

Anisonitrile was prepared according to the method of
Van Es (46). 136g of p-anisaldehyde (1 mole), 80g of
hydroxylamine hydrochloride (1 mole + 15%), 125g of sodium
formate, and lSOOmI of 98% formic acid were refluxed for
one hour. A six fold dilution oF the reaction mixture with

water caused the anisonitrile to precipitate.

5-p-chlorophenvltetrazole: The procedure was the same as for
the preparation and recrystallization of S-phenyltetrazole.
5-o-chlorohenzonitrile was used in place of benzonitrile.
The melting point of 179-1800agreed with that previously
reported (6).

5—o-ch1orobenzonitrile was prepared according to the
method used in preparing anisonitrile. S-o-chlorobenzaldehvde

used in place of anisaldehyde.

S-p-chlorophepyltetrazole: The procedure was the same as
for the preparation and recrystallization of 5-phenyltetrazole.
5-p-chlorobenzopitrile was used in place of bepzonitrile.
The meltinr point of 260-26lo’aoreed with that previously
reported (7).

'5-p-chlorobepzonitrile was prepared accosdine to the
method used in preparine anisonitrile. 5-p-chlorohen2a dchwin

was used in place of anisaldehyde.

sodium salts of tetrazoles: Suspensions of the respective
tetrazoles in water were titrated with 0.10M NaOh. The
tetrazoles dissolved before the equivalence point was reached.
The aqueous solutions of the sodium salts were evaporated
nearly to dryness on a steam bath. The salts were then re-
crystallized from acetone and dried at 1100 before use.

C. Preparation of Metal Complexes

Bis(5-phenyltetrazolato) cobalt(II)monohydrate: A complete
description of the preparation of this compound will be pivcn.
This method applies to all cobalt(II), nickel(ll), zinc(II).
and copper(ll) complexes. In all cases, precipitation occur—
red within a few minutes.

Forty m1 of an aqueous 0.10M solution of sodium S—phenyl-
tetrazolate were added drOpwise to 200ml of a magnetically
stirred aqueous 0.01M solution of cobalt(II) perchlorate hexa—
hydrate. Since the complex was insoluble in most solvents, it
could not he recrystallized.

The pink product was washed six times with distilled water,
partially dried with anhydrous diethylether, and finally dried

to constant weight 13 vacuo over P20 Digestion and prolonped

5.
washing of the precipitate were avoided because Daugherty (45)

had reported that bis(5-phny1tetrazolato) copper(II) monohydrate
was partially hydrolyzed to hydroxo(5-pheny1tetrazolato)copper(II)

by stirring the complex with water for twenty hours at room

temperature.

16
Anal. Calcd. for Co(C7H5N4)2-H20: Co,16.0; C,45.78; H,3.29;

N,31.45; Found: Co,l6.1; C,44.24; H,2.89; N,30.86.

Bis(5-0-Chlorophegyltetrazolato)cobalt(II)menohydrate: This
pink product formed in a few minutes. Anal. Calcd. for
Co(C7H4N4C1)2-H20: Co,l3.5: C,38.SS; H,2.31; N,25.68;

Found; Co,13.3; C,37.65; H,l.91; N,26.06.

Bis(S-n-chlorophenyltetrazolato)cobalt(II)monohydrate: This
pink product formed in a few minutes. Ana1.Ca1cd. for
Co(C7H4N4C1)2'H20: Co,l3.5; C,38.55; H,2.31; N,25.68;

Found: Co,l3.4; C,37.85; H,l.95; N,25.95.

Bis(S-p-methoxyphenyltetrazolato)cobalt(Il)monohydrate: This
pink product formed immediately. The solid turned tan in
color on drying to constant weight. Aggl. Caled. for
Co(C8H7N40)2-H20: Co,13.5; c,44.03; H,3.90; N,25.68;

Found: Co,l3.9; C,42.78; H,3.23; N,25.85.

Bis(5-p-chlorobenzyltetrazolato)cobalt(II)monohydrate: This
pink product formed immediately. The product turned brownish
pink on drying to constant weight. 5231. Calcd. for
Co(C8H6N4C])2'H20: Co,IZ.6; 0,41.34; H,3.0]; N,24.05.

Pound: Co,lZ.5; (3,150.4; H,2.73; N,23.‘M.

Nickel complex of Sap-chlorohenzyltetrazole: This blue-violet

8011d precipitates immediately. Anal. Calcd. for

l7

Ni(C7H4N4Cl)1.8-H20: N1,14.7; c,37.70; n,2.29; n,25-20;

Pound: Ni,14.7; C,37.0; H,2.03; N,25.06;

Nickel complex of 5-p-methoxyphenyltetrazole: This metric
blue violet solid precipitates immediately. Anal. Calcd. ‘or
N1(c8n7N40)1.8-n20: Ni,13.16; C,44.95; H,a.10; N,26.2;

Found: Ni,13.0; C,43.06; H,3.37: N,25.92:

Nickel complex of S-phenyltetrazole: This blue violet solid

precipitates immediately. Anal. Calcd. for Ni(C7l O

{5N4)1.8°“2
n1,15.2; C,43.6; u,2.6]; N,29.1; Found: Ni,15.5: C,44.6;

u,2.82; N,30.l3;

Bis(S-p-chlorohenzyltetrazolato)zinc(IT): This white solid
precipitates immediately. Anal. Calcd. for Zn(C8H6N4Cl)2:

C,42.40; H,2.66; N,26.72; Found: C,42.33: H,2.33: N,25.05:

Bis(5-o-chlorophenvltetrnzolato)zinc(ll): This white nnild
precipitates immediately; Anal. Calcd. for Zn(C7H4N4Cl)2:

C,39.55; H,l.89; N,26.3S; Pound: C,39.78; H,l.80; N,26.SS:

Bis(5-p-chlorophenyltetrazolato)zinc(II) 3/2hydrate: This
white solid precipitates immediately. Anal. Calcd. For
2n(c7uanac1)2°3/2u20: C,37.10; n,2.44; N,26.80; Found:

c,37.16; u,2.78; N,25.07;

l8

Bis(5-p-methoxyphenyltetrazolato)Zinc(II): This white solid
precipitates immediately. Anal. Calcd. for Zn(C8H7N40)2:

C,46.16; H,3.36; N,26.92; Found: C,45.86; H,3.31; N.27.00;

Bis(S-phenyltetrazolato)Zinc(II): This white solid precipitates
immediately. Anal. Calcd. for Zn(C7H5N4)2: C,47.20;1H,2.82;

N,31.4S; C,46.95; H,2.69; N,3l.53;

Bis(S-p-chlorobenayltetrazolato)copper(II)trihydrate: This
blue-violet solid precipitates immediately. Anal. Calcd.
fOr CU<CBH6N4C1)2.3"20: CU,12.57; C,39002; H,3.58; N,22.16:

Found: Cu,12.37; C,38.40; H,3.41; N,22.43;

Bis(S-o-chlorOphenyltetrazolato)copper(II)monohydrate: This
light ereen solid precipitates immediately. Anal. Calcd. for
Cu(C7H4N4C1)2'H20: Cu,14.39; C,38.10; H,2.28; N,25.39;

Found: Cu,14.66; C,37.47; H,1.58; N,25.41;

Bis(S-p-chlorophenyltetrazolato)copper(II)monohydrate: This
light blue solid precipitates immediately. Anal. Calcd. for
Cu(C7H4N4C1)2'H20: Cu,14.35; C,38.11; H,2.28; N,25.39;

Found: Cu,14.37; C,37.01; H,1.98; N,25.32;

hydroxo(S-p:methoxyphenylterrazolato)copper(ll): This lioht
blue solid precipitates immediately. A221. Calcd. for
CU(C8H7N40)(0H) Cu,24.82; c,37.53; H,3.12; N,21.88; Found:
Cu,25.01; C,37.68; H,2.93; N,22.20;

19

Hydroxo(S-phenyltetrazolato)copper(II): This dark blue solid

 

precipitates immediately. 523;. Calcd. for Cu(C7HbN4)(OT):
Cu,28.12; C.37.20; H,2.67; N,2§.80; Found: Cu, 28.05; C,36.91;
H,2.3l; N,24.82;

‘Bis(S:phenyltetrazolato)copper(II)monohydrate: This complex
could not be prepared from aqueous solution. It was finally
prepared in methanol by a method previously reported by
Daugherty (45). When methanol solutions of CuSo '5 H 0 and

4 2

S-phenyltetrazole are mixed in any proportion, Cu(C7li5 Z)2 hzo

precipitates from solution after several hours. Anal. Calcd.

for Cu(C7l 0: Cu,l7.l; Found: Cu,l7.3;

S M4)2 2
Attempted preparation of his(5-p-methoxyphenyltetrazolato)
copper(lll:

Daugherty was unable to obtain this complex from
methanol solution. Instead, he obtained a mixture which
yappeared to contain Cu(C8H

N40)(0H) and Cu2 (C8 0) 280 Ely”.

7 M7 2 4.

In the present investigation, Cu(C8 H O)(Oh) was obtained

7IV 4

instead of the desired product.

flydroxo bis(S-p-chlorobenzyltetrazolato)chromium(llI)tetrahydrate
The procedure for the preparation of this complex will

be outlined in detail. The other chromium(lll) complexes

were prepared in the same manner. 60.0m1 of aqueous 0.10M

sodium 5-p-chlorobenzy1tetrazolate was mixed with 200ml of

20

anueous 0.01M chromium(TII) perchlorate hexahvdrete. Tnitiallv,
the solution changed from dark green to yellow green as the
reactants were mixed. After three minutes, 5-p-ChlorohenZVl—
tetrazole, a white solid, precipitated From the solution.

The S-p-chlorobenzvltetrazole was removed by Filtration and

the filtrate was retained. Another 60.0ml of aqueous 0.10%
sodium 5—p-chlorobenzv]tetrazolate was then mixed with the
filtrate. After a Few minutes a pinkish-violet solid precipi-
tated from the solution. Anal. Calcd. For Cr(C8H6NA(l)2
(Oll)-4|120: Cr,9.8; C,36.l: li,3.98; N,2l.15: Found: Cr,‘).lt;

C,35.S; H,3.42; N,21.]3;
dydroxo big(S-o-chlorophenyltetrazolato)chromium(TTT)tetrahvdrnte

S-orthochlorophenvltetrazole did not precipitate From
solution. After an hour, the erey complex precipitated
from solution. Aflii' Calcd. for Cr(C7H4N4Cl)20H-4H2O:
(2r,10.14; (2.33.62; ll,3.40; N,22.S; Found: Cr,]0.0; C,33.l6;

H,2.3l; N,21.92.
Hydroxo bis(S—n-chlorophenyltetrazolate)chromium(lTT)Eetrahvdrntv:

This prey solid precipitated within four hours after the
5-p-chlorophenyltetrazole was removed by filtration. Anal.
Calcd. for Cr(C7H4N4Cl)ZOH-4"20: Cr,]0.4; C,33.62; U,3.40:

”.22.5; Wound: Cr,l0.0: C,33.54; H,2.64; N,21.9l.

21

Hydroxo his(5-p-methoxyphenyltetrazolato)chromium(III)

hexahydrate:

p-Methoxyphenyltetrazole, a white solid, precipitated
immediately. The grey complex precipitated from the filt—
rate within a few minutes after the addition of excess .10M_
sodium S-p-methoxyphenyltetrazolg3 £231. Calcd.
Cr(C8H7N40)20H-6H20: Cr,9.9; C,36.3; H,5.22; N,21.21;

Found: Cr,9.S; C,35.3; H,4.03: N,21.04.
Hydroxo bis(5-phenyltetrazolato)chromium(III)tetrahydrate:

S-Phenyltetrazole did not precipitate from solution.
The pinkish violet complex precipitated from solution within
four hours. The analytical data indicate that it contains
impurities. 522;. Calcd. for Cr(C7H5N4)20H 4H20: Cr,12.2;
C,32.80; H,4.43; N,26.S7; Found: Cr,ll.5; C,39.ld; H,3.68;

14.25.99.

Attempted preparation of manganese(II)complexes: No color
change or precipitation occurred when aqueous manganese(II)
solutions were mixed with aqueous solutions of the sodium

S-substituted tetrazolates.

_§ttempted preparation of iron(II) or iron(IIT)comp1exes: In
all cases small quantities of an orange solid, probably ferric

hydroxide, precipitated from solution.

22

D. Analytical Methods

Cobalt: weighed samples of the cobalt complexes were
decomposed by heating the solids with aqua repia. The result-
ine blue-green solutions were evaporated to dryness on a hot
plate. The residues were reheated with aqua rcpia and the
solutions were evaporated to drvness. This process was
continued until the residues were completely water soluble.
The pink residues were then dissolved in water and the re-
sulting solutions were made slightly acidic (pH 6). Murexide
indicator was added and the pH of the solutions were adiusted
with ammonia until the color of the indicator chapped From
orange to yellow. The solutions were then titrated with
0.01001” ethylenediaminetetraacetic acid (EHTA) to a color
chance from yellow to violet (47).

Nickel: Only one of the nickel complexes could be
titrated with EDTA. Evidently, the tetrazolate anion is in-
completely destroyed by nitric acid and interfers with the
color change of the indicator. Thus,thc nickel samples
were analyzed hv the cyanide method. Heiehed samples were
treated with 20ml of 0.1068M KCN solutions, Sml.ef concen-
trated aqueous ammonia, and lml of a KT solution containin"
1.19 of K1 per ml of solution.

The samples were allowed to stand overnipht. The
complexes dissolved to eive pale yellow solutions. The

excess cyanide in the sample solutions was titrated with

23

0.100M A8N03. Silver nitrate dried at.110° was

used as a primary standard. The.0.l068MAKCN solution

was standardized with the 0.100M AgNO3 solution.

Daugherty (45) found that titrations of known nickel samples
in the presence of tetrazole resulted in an error of less
than 2%.

Copper: Only a few of the copper complexes could be
analyzed by EDTA titration due to interferences in the color
change of the indicator.

All of the complexes could be analyzed by atomic
absorption spectroscopy. Samples for atomic absorption were
dissolved in ammonia and were diluted to volumes such that
the solutions contained less than 10 ppm of copper. All of
the solutions were stored in plastic bottles to avoid
contamination by impurities in glass or pyrex. Standard
solutions containing 0 to 10 ppm of copper(IT) ion were
prepared from aqueous 0.009898M Cu(ClOa)2'6H20 solution.

The aqueous Cu(C104)2°6H20 solution was standardized with
0.01001M EDTA. Analytical results obtained by the atomic
absorption method aereed very closely with those that could
be obtained by EDTA titrations.

Chromium: Samples For analysis were decomposed by
heating the solids with aqua regia. The resultina green
solutions were evaporated to dryness. The residues were

treated several times with aqua regia. The excess chloride

24
ions, not used in complexing the metal ions, were precipitated
with silver nitrate solution. The AgCl was removed by filtration.
The Chromium(III) ions were then oxidized to dichromate ions by
4)28208
and 0.10 H NH4N03. A few milliliters of 0.1OAgN03 were added

to catalyze the oxidation. The oxidation was complete within

the use of 5.0 ml of a solution containing 0.10 M (NH

five minutes. The oxidized samples were diluted to volume
with enough water so that the absorbance values at 445 nm were
less than 1.0 when 10.0 cm cells were used. The samples were
compared against standard dichromate solutions which obeyed
Beer's law at 445 nm.

The dichromate standard solution ranged in concentration
between 0.0002 N and 0.0014 N and were prepared from a
0.009819 N K CrZO solutidn. The 0.009819 N K Cr 0 solution

2 7 2 2 7

was prepared by using KZCr207 as a primary standard.

Carbon, Hydrogen, and Nitrogen Analyses: The carbon,

 

hydrogen and nitrogen analyses were performed by the Micro—
analytical Laboratory of the Institute of Water Research,

Michigan State University, East Lansing, Michigan.

E. Magnetic Moment Measurements

 

Magnetic susceptibilities were measured by the Couy
method by use of methods similar to those described by Vander

Vennen (48). However, the apparatus was modified in order to

25
allow a constant stream of helium to pass over the sample
tube. Thus, water was prevented from condensing on the
sample tube at low temperatures and the sample was protected
from hydrolysis.
The calculation of the magnetic moment wasnade by the use

of the equation: (49)

(

lo’x = F' x "’

W

 

s (1)
where X is the gram-susceptibility of the sample: F' is the
force exerted on the sample alone, i;E;’ the measured force
corrected for the force experienced by the tube alone; NC; is
the weight of the sample in grams; and B is the tube constant,
for a given magnetic field and a given temperature.

In practice, each 8 value must be determined for a parti—
cular tube by use of a material of known susceptibility. F'
values are obtained at several magnetic fields and at several
temperatures. At a given temperature, the X value of the
calibrant will be constant and will be independent of the
magnetic field. The F' values, however, are dependent on
the magnetic field at a given temperature. Therefore, a P
value can be calculated for each magnetic field at a given
temperature. Since x varies with temperature, other B values
can be calculated from F' values at other temperatures.

In this work, hg[Co(SCN)4] was used as a calibrant. Its

susceptibility is 16.44 x 106 cgs units at 2930K and it obeys

26
the Curie-Weiss Law, xg o(T + 10).1 where T is expressed in
degrees absolute. Figgis and Nyholm (50) reported that

Hg[Co(SCN)4] is a much better calibrant than CuSO ~SH°O or

Z.

Fe2(NH4)2(SO o6H20.

4)2

The molar susceptibility, Xm' of the sample is obtained
by multiplying the gram-susceptibility bv the molecular weight.
The susceptibility of the metal ion, ym' is obtained by correcting
the molar susceptibility for any diamagnetic species present.
Pascal's constants (51) were used to estimate the diamagnetism
of the ligands and cations.

:

In normal paramagnetic substances, Xm related to the

absolute temperature as

x = % Curie Law (2)
or

x'= C

TT_:37_ Curie-Weiss Law (3)

For the latter case, a plot of l/xm' against T allows evaluation
of 0 from the intercept.
The magnetic moment u of the sample may be calculated
from the molar susceptibility by
u = 2.84 (T x xm')l/2 (A)
The low temperature studies were performed by using a

specially constructed Dewar flask similar to that described

by Vander Vennen (48). The magnetic moments were measured at

27
0 , 0
room temperature, 195 h, and 77 K.

F. Spectroscopic Measurements

 

The infrared spectra of the complexes were obtained by
use of nujol and hexachlorobutadiene mulls, a Perkin Elmer
Model 457 spectrophotometer (4000 cm -1 to 250 cm-1) and a
Perkin Elmer Model 301 SpectrOphotometer ((80 cm-1 to 167cm-1).
Cesium iodide and polyethylene plates were used. The visible
and ultraviolet solution spectra were obtained by use of a
Cary Model 14 spectrophotometer.

The near infrared, visible and ultraviolet spectra of
the solids were obtained on a Beckman Model DK-Z spectro—
photometer (equipped with a reflectance attachment) at Dow
Chemical Company, Midland, Michigan. The spectra were also
obtained by the method of Cotton and Coodgame (52) by use
of a Cary Model 16 spectrophotometer. In the Cotton and
:oodgame (52) method, a nujol mull of the complex was painted
onto a sheet of filter paper. The sheet of filter paper was
then taped to the exit window of the sample compartment.
Another sheet of filter paper was painted with nujol and this
sheet was taped to the exit window in the reference compartment.
The nujol mull method was generally quite satisfactory for
bands in the ultraviolet and visible regions but gave rather
poor results in the near infrared region. The major advantage
of the nujol mull method lies in the accurate location of hand
maxima by use of the slowest scan rate on the Cary Model 14

spectrophotometer.

28

The electron spin resonance spectra of the powdered
complexes were obtained at temperatures from -l60O to 250
by dse of a Varian E-4 EPR spectrometer equipped with a
Varian E-257 variable temperature controller. Powdered
samples were diluted by precipitating the zinc complex in

the presence of copper(II), cobalt(II) or chromium(III)

ions.

DISCUSSION OF RESULTS

 

From the analytical data, it appears that each cobalt(II),
nicke1(II), chromium(III), copper(II), and zinc(II) ions
can only accommodate a maximum of two tetrazolate anions when
the complexes are precipitated from aqueous solution. It is
rather surprising that chromium(III) does not form a 3:1
complex. Apparently, the hydroxide and the tetrazolate anions
compete in aqueous solution for the coordination sites on
chromium(III). The 3:1 complex can possibly be prepared and
precipitated from nonaqueous solutions by using tetralkyl-
ammonium salts in place of the sodium salt.

C0pper(II) also forms hydroxo complexes. Daugherty (21)
could only prepare bis(S-pheny1tetrazolato) copper(II) from
methanol solutions. Only impure bis(S-p-methoxyphenylte-
trazolato) copper(II) could be obtained from methanol solu-
tions (21).

As previously observed (22), niekel(li) forms complexes
with a tetrazolate to nickel(II) ratio between one and two.
Perhaps the complexes are 2:1 complexes with tetrazolate
vacancies in the crystal structure.

The solubilities of these complexes are listed in Tables
I to V. All of the complexes are insoluble in acetone, 1,4-
dioxane, methylenechloride, benzene and acetonitrile. Only
bis(S-p-chlorobenzyltetrazolato) copper(II) trihydrate is
soluble in nitromethane. Some of the complexes are even

insoluble in dimethylsulfoxide, methanol, N,N-dimethylformamide

29

30

and pyridine. Of these solvents, pyridine, dimethylsulfoxide,
and N,N—dimethylformamide seem to be most suitable to dissolve

the solids for measuring solution spectra.

Infrared Spectra
Comparisons of the infrared spectra of the tetrazoles
and their respective sodium salts and complexes are shown in
Tables'VI to XV. Band assignments were based on the results of
a normal coordinate analysis on sodium tetrazolate
monohydrate (32) displayed in Table XVI. Table XVII shows
the assignment of bands in sodium tetrazolate monohydrate (32).
Complexes containing water of hydration display bands
in the 3350 to 3500cm"1 spectral region. Many of the sodium
salts also contained an O-H stretch in their infrared spectra
even though the salts had been dried at 110° for several
hours.
The spectra of the tetrazoles and their respective
sodium salts and complexes are quite similar with the exception
of bands in the 2700-2850cm'1 spectral region. Bands in this
region have been previously assigned as N-H stretches. (19)
This assignment was further confirmed by Helm (31) who compared
the spectra of 1-H-tetrazole and l-D-tetrazole. No bands were
found in the 2700-2850cm"1 spectral region for 1-D tetrazole.
Due to the absence of the N-H stretch in the spectra of the
complexes and the sodium salts, the tetrazoles appear to

coordinate as the anion.

31

As a result of a normal coordinate analysis by Carber,

33 _l., it appears that none of the infrared bands can be
assigned to C-N and N—N stretching modes in contrast with
previous assignments (23,31,53).

Despite the similarities in the Spectra of the sodium
salts and their respective complexes, the spectra of the
sodium salts often contain additional bands. Jonassen (23)
has postulated that fewer bands are found in the infrared
spectra of the complexes than in the infrared spectra of
their respective sodium salts because of the loss of re-
sonance character in the complexes. Although all of the
fundamental bands appear in both the sodium salts and their
respective complexes, coordination of tetrazoles with metal
ions often reduces the intensities of overtone and combination
bands. Occasionally, more bands appear in the spectra of the
complexes than in the spectra of the sodium salts or the
tetrazoles. In these cases, coordination may cause a splitting
of bands in the 4000 to 650cm-l spectral region. This splitting
of tetrazole bands also accounts for extra bands found in
the far infrared spectra of PMT complexes in the netal-lirand
deformation region (178-236 cm-l) and the metal-nitrogen

stretching region (250-450 cm_1) (55).

The infrared spectra provide little information about
the presence of perchlorate since the tetrazoles or sodium
tetrazolates themselves have bands in the 620—630, 932, and
1090 cm”1 spectral regions which have been assigned as ionic
perchlorate bands (54).

The far infrared spectra have been very useful in demon-
strating metal-ligand interaction in tetrazolate (11) and
PMT (55) complexes with copper(II). In most cases, the infrared
bands of the tetrazoles in the 4000 to 650 cm-1 spectral
region are unshifted on complexation (55). However, D'Itri
(55) found that bands in the 180 to 360 cm.-1 region are
shifted to higher frequenty on complexation. Furthermore,
the frequency of a given band in the infrared spectrum of
PMT was increased in frequency with a decrease in the ionic
radius of the metal ion. Similar frequency shifts were ob-
served in the present study as shown in Tables VI, VIII, X,
XII, and XIV.

Sharp, 55,31. (56), Jungbauer and Curran (57), HeWinnie
(58), Coldstein, _£ _1. (59), and Clark and Williams (60)
have tentatively assigned bands in the 250 to 450 cm-1 region
as the metal-nitrogen asymmetric stretches for transition
metal complexes of substituted anilines, aniline, 2,2'

bipyridylamine, heterocyclic bases, and pyridine respectively.

33

D'Itri and Pepov (55) and Garber, _£ _1. (32) also observed
bands in the 250-320 cm"1 spectral region which they assigned
to metal-nitrogen stretching frequencies.

In 1966, Frank and Rogers (61) compared themetal-nitrogen
stretching frequencies for various copper(II) complexes of
substituted-pyridines and listed these ligands in probably
order of increasing donor strength. The ligand giving the
largest metal-nitrogen stretching frequency was considered
the strongest ligand.

A comparison of the far infrared spectra of the copper(II)
complexes of the various S- substituted tetrazoles and their
respective sodium salts indicated that only a few of the
bands could be tentatively assigned to metal-nitrogen stretching
frequencies due to the presence of broad unresolvable bands.
Clark and Williams (60) also found that the far infrared
spectra of the polymeric octahedral complexes MClZoZ pyridine
(M 8 Mn, Fe, Co, and Ni) consisted of broad badly resolved

bands in the 200 to 260 cm“1 spectral region. The far infrared

spectra of the complexes are displayed in Figures 1-5.

34

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oHnaHom 2Houmuoooe I
mHnsHow I

oHesHomsH I

O
5.4
m

HUIUJU)

 

 

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H H H H H ocmssom

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m.Hm m m w m mvHEmEuomesueeHolz.z
a H H H H acaoncxa.H
m.Hm m m m m mpHxOHHamHmzuoeHo
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emm um muco>Hom maoHuo> CH moerezoo AHHquosou was we muHHHnsHom .H eHsob

35

q

 

 

 

mHnuHOu >Huueuoo h I m.e
mHsaHtm sHsecHHu I H.Hv
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36

oHnsHOm meumuonoa I

 

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nos

 

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meaHom mHuanHm I m.Hm
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H H H H H osmoneua.H
m m.E m «.5 m ovonHHathsueEHa
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oNN

um mucw>Hcm msonm> cH mmoncho HHHHV EDHEousu

ecu Ho saHHHnchm .>H «Hams

38

 

 

 

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mHozHcm zHuszHm I m.Hm

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02335 I H
H H H H H mHHuuH:0uoo<
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H H H H H meHHcHzomcoHsaum:
m m m e H mcHwHuzm
H H m H H Hocmcumz
H H a H H oeHsmeHoHHsaaoeHoIz.z
H H H H H ocmonaIa.H
w w w H H mvonHHamHmnueEHa.
H H H H H measuoEouqu
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azommosmaeHeIeIn HzoszoocHzoIcIm Hzoa=eoHoIeIn azoamsoHeIoIm szonzooIm
.NN Hm mucm>Hcm macHHm> cH mmmecsoe HHHV ucHN as“ e0 saHHHpchm .> «Hews

39

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Hmmcsb n 2H mucxucwe cH execs we :uwmeum

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.xch

>um> I.3> .xmos u 3 .EwacE n E .ucowum I my mHmocucwumc cH moHuHmmeucH m

Hsaflmvoeem

 

Havossa
HavoHom Hsvcaom Havomom Havoaom HavoaaH Hsaxmvoocm Havowaa
Havomcm Havosom Havoeom Hmvcscm Havosom Havomom Hevcmom
HevmmHH HstNHH HEVONHH HavomHm HEVOHHH HH_HmvosHm HavoaHH
HEVOHNH
H;_Hmvoosm HHHHmVocam Hs.Hmvoosm Ha_HmvoHHm
Havomam Havoomm
Amvosmm Havoomm
Havossm
o~:H.HmoVaHeo NHHVcN omm.NH=o oN=.w.HHHz om:.~soo emz Hm

 

eumHowmpuouH>cm£eIm EsHpom .eHoumwuoqucmneIm we muuomem woumuwcH

HIEumoH Cu oooq Eouw mHHsz ecchmuoa
Ioonmumxm: was HoHaz :H chwmuuouH>ceceIm we mmwaeEcu msoHum> mam

.H> magma

40

coscHucoo

 

 

Hs_HavoamH HEVCHHH HavosmH HmVCHHH HEVOHHH HavoHHH
HLHHavoNeH HevcHoH HsVoNeH HEVOHsH HavoosH Hs_HmvoHsH HmVoHsH
HavcoHH _;_HsvoHHH HevcoHH HavomsH HavanH
Hp_HavooHH
HavomHH
AsconH HavcawH HavonH HzVonH HavonH szcsmH Hs_HevommH
HEHHNHH
HpaHaVoHaH H;_AsvmsaH Hs_szosaH HHHszommH Hn_xzvomsH HsaxavoHaH HaHHHHH
Havooom

Havoamm
_n_xmvoss~
Hs_HmvomHH
HIVOHHH
cmmq.xmovmsuu HHHVcN o~=.~sse c~m.m.HHHz c~=.~Hcc Hex H:

 

woacHucou I

ow> mHsmP

4]

wmscHucoo

 

 

Havoon Havoon HEHHHOH HavoHOH HavomoH H3>VomoH HmHHHOH
HavocHH HavooHH H2VOOHH HavooHH HaHOHHH HsvaHH HaemOHH
HavoaHH HavomHH HavoNHH HavomHH HEHHNHH
HavesHH HavHsHH HstHHH HEVOHHH HavoHHH
HavoHHH HavHHHH HEVOHHH HEVOHHH HavoHHH HmHoHHH
Ha>v HHH HavoaHH AEVONNH HavmmHH HavooHH HavooNH
HavomNH HEVOHHH HavoeaH HsvHHNH HsvquH HsHooaH HavoHNH
HavowHH HavomNH HavomaH HavomaH HEVOHHH HavomHH HavoaaH
HavosmH HavoamH HavosmH HavosmH HavoamH HavosmH
Havome HavoamH HavoamH HavommH HavooaH
HmvcmaH Havoqu HavoeaH HmVoHHH HmVoHHH HavomaH HavonaH
AmHoHHH HavquH HavoeaH HavosaH HmHoHaH
HsVoHHH HavoamH HEHOHHH HavommH HavonH Ha>vm~mH HavoomH
om:H.HmcvaHHo HHHVcN o~z.~eao o~:.w.HHHz oN:.NHco Hmz am

 

ewacHucce I .H> ”Home

42

cesoHusou

 

 

Havens Hmvmss Havoos
Haemaa Amooss
Haaows Havoas Havens Amocoo Havoas Haemwo Haynes
HmHHoH HavooH Havoos
Havens AmVoHH Havoas Havana Havens HmHHHH HmHHHH
Havoma Havoms Havoas Havana Havoaa Havoas Havoms
Hsaxavomm Hs_H3Homm _H_H3vomm Havana HHHHaHoaw Havoow Havens
HavoHa Havon HsVONH Havoaa Havoaa HavoHs Havaam
HH_H3Hoea Hpaxavomm Ha_Hsvosa HHHszmam HHHHavoaa .nHHzHoma Havama
HeHoHoH HEHHHOH H3VOHOH HeVOHoH HeHoHoH HaVoHOH HeHHHoH
HanHoH Havoqu HsveHoH HsvwaoH HavaoH HanHoH HsHaHoH
HsHoHoH HavoooH HeHoHoH HsHoHoH HsHHHOH
onH.Hmcv~HHe NHHVcN o~:.~H=e oH:.m.HHHz o~m.~ch Haz H:
soacHucou I >H meaH

43

 

 

HsvcmH HaHHsVomH HQHAEVOHH HavomH
HavoaH Havacm Hevsom AcmvHCN
Havon HaveHH HeVeHN HLHHmvHHN
Havaam Havamm HIEUHHH ea oHN
“can; seas
HsvaH Hatm>om Hamvoma HachHH
Havama Havasa Assess Heaxzvcam Hp_Hqum~
Haemaa HmvHom Aavmom szsom
Havmmm Amvch HH_HzVaN HavHam HsHHemem
Hmvmmm
Havmwm Asvcca Havemm Hmvsam Hevmmm Hsafiavmam
AavaH Hsvsma Havoma Heavens Hamvsoa
szsms Asvmma Hevmaa Hevmma Havana HauHmvmsa
Hevmcm szHHH HevHHH HmVHOH Havosa
Haexevamm Hevmmm Havamm Hechm Hamvosm
Heuvosme HemvaHoe szmHs HemvoHe
CN:H.H:cv~HHe «ecu o~s.~s=u c~:.m.HHHz 0N:.msou sax s:

 

emscHacou I .H> mHsaH

LHJ

44

Table VII. Infrared Spectra8 of 5-Phenyltetrazole and Sodium

S-Phenyltetrazolate with Band Assignments

 

 

Genuine
hT NaT Vibrational Assignment
Node
3690(9)
3560(m) 3570(5) [“1 + V11)
3500(s)
3370(s)[b] V13 O-H stretch
3210(m)
3140(m)_ 3160(s)[b] ”1 ring c-n
3050(m) 3050(5) [“2 + 1600]
2980(m) 3000(s)[b]
2760(3) “14 [N—H stretch]
2660(s)[b]
2590(5) 3]

2530(s)fb]

2000(m)
1965(m)
1923(m)
1850(m)[b]
1780(w)
l760(w)[bl

2290(w)

1950(w)[b]

1860 (w)

+V51
2 + 8]
+V81.
2 3v10]
V7 + 10]
8 + 10]
4

C

V V

[2
[V
[V
[V
l
[
[
[ + 9i
[V5 + V9]

 

a Units are in cm-

b Brackets

indicate possible assignments

Continued

45

 

 

Table VII. - Continued
Genuine
"T NaT Vibrational Assignment
Node -

1730(w)[b]

1680(m) O-H bend
1610 1610(m)
1570(s) 1560(m) [ V9 + V10]
1500(m) 1525(vw) I v7 + v11]
1470(s) 1460(s) V2 ring deformation
1430(w) 1450(5) V6 C-H in plane bend
1400(s) 1380(m) [ V10 + ”12]

1360(m) [ V10 + V11]
1290(m) 1290(m) V3 rino vibration
1260(m) 1260(w) V9 + V12

1200(m) V9 + VII

1170(s) V4 ring breathing

1130(m) [ V12 + 650]

1125(m) [ V12 + 615}
1103(w) 1105(w) [ 011 + 650]
1087(s) 1090(vw) [ V11 + 615]
1057(m) 1070(m) V5 ring deformation
1036(m) 1025(m) V7 ring deformation
1015(m) 1010(m) V8 rinzdeformation
994(s) 980(w)[b]

[ V11. + V12]

 

Continued

Table VIT.

- Continued

46

 

 

Genuine
HT NaT Vibrational Assignment
Mode
924(w) 910(w) v10 4 C-H out of plane bend
850(m) 860(m) I v12 + 350]
796(m) 780(m)
725(5) 725(3) v9 ring deformation
700(3) 700(5) [2(355)]
685(3) 685(5) I V4 - V11]
670(s) 675(8)
660(m) 665(3)
540(sh)
490(5) 505(3) V12 out-of-nlane ring bend
449(w)[b] 459(s) v11 out-of-plane ring bend
407(sh) 420(sh) [ V2 - V7]
345(w)[b] 355(m) I V5 - V91
307(w) 308(w) . I V7 - V9]
250(sh) I V9 — V11]
207(sh) [ V10 - V9]

108(3) ‘ l70(s)[b]

 

47

 

 

 

(I ll ll
7 6 4
I I l I l I I
J"\
I I I l l I 1
Co(C7H5N4)2-H20
4 l 1 ' I I

 

N1(C7”5N4)1.8."20

 

Cu(C7H5N4)2.nzn

J. I I

1 L l
2n(c nrn ) \VVV vf\//V\
7 3 4 2 .
.‘V/V \ / \/‘\v\
I I l I l

 

 

 

 

 

J
Cr(C7N5N4)2(0H)°4H20 .J’k
L l L l 1 I
100 200 300’ 400 500 son 7uo
cm'1
Figure 1 Far Infrared Spectra oF S—Phenyltetralole,

Sodium S-Phenvltetrazolate and Various
Complexes of Sodium S-Phenvlretraznlnrr

48

.H> emcee pcoecH com I m

UQDCquOU

 

_;_Amvo<cm
_£_HmvosHN

_L_Hmvomam

HH_HmVoHs~

_2_Hmvomau

 

Havcocm Havocom Havooom Havooom Havooom
Havomcm Hemvoaom
_a_HmVomom Havoaom Hn_Hmvcon _s_Hmvomom Hemvomom HamvooHn
HavoeHH Hs_xmvosHm
Asmvooam HemHOOHH Hemvooan Hamvoomm Hamvooam
_n_Amvooam Haaamvoosm _a_HsVooan HH_Amvoosn
Havoosm HeVoHHH Hamvoosn Hamvoomm HavoHnn _n_HaHoHHm
o~m0.HmchHHc . Hess HchHHvsc o~:.m.HHHz o~x.~sce Hmz a:

 

HIEo 59H Cu HIEo coca Eouw mHHaz
ecoHpmuoeouoHcooxoz pee Henna :H mHonmuuouHzcmce>xozuezIeIn
we mmerchu maoHuma was oHowmuuwuHacoccmxcnumZICIn
EaHpom .chNoHueuH>coxc>xozuerlolm Ho muuoocm puumuucw
m

.HHH> MHDMH

49

omscHuccg

 

 

HmVOHHH HuvchH HEVONQH HcVoNsH szmHsH HEVQHHH HavousH
HavoosH HavooHH
HaVOHHH
HavonHH
HavoHHH
_s_HavoowH Hs_szoomH
Havome HsvamH
HavommH _n_H3vooaH HavoHaH HHHHavonH
Hs_HaHoHaH .s_H:HoHHH
_n_H3Voao~ _n_H3Voao~ Havomoa
Haeommm
Havomsa Haixevoonm
HuvcHHN Havommm _L_H¢Hoos~
c~=s.HmcvaHo NHcN Hzovsze c~:.e.HHHz o~:.~Hce Hex H:

 

pmscHusoo

.HHHD mHan

50

poocHucoo

 

HavoaNH HavomHH HavomaH HavoaaH HavmmHH HavcoHH HavoomH
HavoomH HavoHHH HavoomH HavooHH HavoHHH HavoomH
HmvcmmH HEVOHHH HmVonH HaHoHHH
HavosmH _p_HevoomH HHHHeHoHHH HavosmH nufiuvoonH
HsVoHHH HmvHaHH HavownH _a_HeHomnH HavomHH HavonH HavomnH
HavoHaH HcmvmaaH HavnoaH HavoHHH
HavoaaH HmvHHQH HmHoHHH HnHoHHH. HavoasH HmVOHHH -HuHoHHH
HmvHHsH HmvmsaH HavooaH HavosaH HavnnaH HmHoHHH HaHoHHH
HHHHHHH. HaeosaH
HavoomH HeVoHHH _n_HaVoHHH HavoonH HeHonH
HEVOHHH HavoamH HaemanH HavoaHH HavoamH HEHHHHH HmHoHHH
HavomHH HEVOHHH szmmmH HEVCHHH HavomHH HmvHHHH HavoaHH
ONxH.H:cV~HHu HHcN Hzcvsso o~=.m.HeHz o~=.~Hco Hmz H:

 

coocHuccu

.HHH> 0H£mb

51

peocHucco

 

HanHOH HmvaoH HstHOH HavoaoH HmVOHOH AmvmaoH HavomoH
HevcHoH HavoaoH HsVoHoH HavoHOH HeHoHoH Ha,oHOH HavoHoH.
HonHoH HavoHoH HavoooH HavosoH HavooOH Hs>vom0H HavoHoH
HavomoH HavooHH HEHOOHH HavooHH HevHoHH HavooHH HavoaoH
HmHoHHH AeVoHHH HmHoHHH HsVOHHH HavoHHH HavonHH
HavoHHH HEVOHHH H3>VomHH HavomHH HavoHHH HavoaHH
HavosHH HavoaHH HavoaHH HavoaHH HavoaHH HavosHH HavomHH
HavosHH HavooHH HaHoHHH HonHHH HaaHoHHH HavoHHH
HavomHH HavomHH HavomHH HmHnHHH
HaemoaH HavooNH HaemoaH HmVoHNH Havmo~H HavoaHH
HmHoHHH HavomaH
HavosaH HavommH HavoHNH HavomaH HavomHH HavonuH HuHoHNH
ouxo.fimovmeuo menu Hzovsso o~=.m.HHHz o~=.~sou Hmz a:

 

zeaaHucou

.HHH> chwb

52

poacHucou

 

 

HmVoHo Havens HEVOHH Havoms Havens Hevcse Havooo

Assess HEVHQH

Havooa HEVHHH HevsoH

Havoma AeVmNH AEHOHH Havoaa HEVOHH HavoHH Havoas

Havens

Havoss Hmvcsa Havoaa Havosa Havens Havess Havens

Havoak Havoms Havoaa Havoaa Havesa HavoaH Havon

Havomm Havens Havana Havens Havana Havana Havoam

Havens Havens Havomw Havomm Havosm

Havomm Havosm Hs_H3>Vomm Havoam H3>Vomm Havens

Assess lexavoom Hsaxmvoma Havoam Havens

Assess Hp_H3voma Havana Havowm

HavoooH .HevoooH HavoooH HavoooH HavoooH HavoooH HavoooH

owes.HmoHHHHo NHHN Hzcvsao o~=.m.HHHz oax.msoo Hmz H:

CQ:CHucoo I H-> mHLwB

munQDCVUCCL

 

HLHAmeqm

Haaxzvmmm

 

 

Haafimvomm Havoem Havosm
Assess Hemvoam Assess Hs_fizvaem HsixsvHeN Haemaa

Havamm Hsaxmvsmm Haifizvoem Havawm

szmam

Hsvam Hmvam Havamm Aevsom
szmqm Hemvomm Hs_xevmmm Hsvmsm HEHHHH HevNHm
Hsvcam Havaoa Havoom Hamvqu Havana

3 Havmma _:_H2Vama
5 H:«vsma Haveea AmVeHa Haemos HnaHsvmma Hmvsaa Haynes
HuvHom HemvHom Asasms Amvsaq Havaaa
Hmaflevamm Havosm HmeNm Havamm Hevsmm Havomm Hmvmmm
szcmm

HmvHHs Huvmma HIVcHa HIVHHs HmVaHs HmvHHs Assess
HIHHHH Assess HsvHHs
om:H.H:cva»e NecN HecVAHvse omz.:.HHHz oN:.uHoe Hm: H:
emscHuaco I .HHH> oHsmH

r)

 

 

H3>VHHH HavowH HavamH HmvaH
HavHaH HaemaH HmvHaH
Hevmoa Havooa
Hs>vHH~ HaaxsvaH HevaH
came.HecvaHo mace AchHsvse om:.m.HHH: o~:.msco Ha: H:

 

woscHucou I

.wa> mHan

Table IX.

55

a
Infrared Spectra of S-p-Methoxyphenvltetrazole and
Sodium S—p-Methoxyphenyltetrazolate

 

 

Cenuine
HT NaT Vibrational Assignment
Mode ~_ _‘

3500(m)[b] 3570(3) [VI + “111

3400(s)[b] v13 O—H stretch
3200(sh) 3200(sh) 1620 + 1585

3160(s)[b] V1 ring C—H stretch
3100(sh) 3080(sh) [ V2 * 16001

3040(sh)

3000(m) I2(1 V2)]
2780(s)[b] V14 [N-U stretch]
2650(s)[b]
2600(s)[b] [2( v3)]
2500(s)[h] I “2 + ”5]

2280(w) I “3 + V8]
2080(w) I2( V7)l
1950(w)[b] I “5 + “10]
1910(w)[b] 1920(w) I 98 + “10]
1870(w) 1880(w) I “A + V9]
1800(w)[b] I2 “10]
1170(w) I ”5 + \b]
1730(w) I V7 + lsl
1710(w) I V8 + V9]

A

a Units are in cm‘]
b Brackets indicate possible assignments

Continued

56

Table IX. - Continued

 

 

nenuine
HT NaT Vibrational Assignment
Mode
1700(w) 1690(m) [ V1 - v2]
1620(s) 1620(m)
1590(5) 1585(3) [ V9 + v10]
1520(9) 1535(m) I ”5 + V11]
1480(m) I “7 + V11]
1480(5) 1450(5) “2 ring deformation
1450(9) 1440(s) v6 c—n in-plane bend
1420(3) [2(700)l
1380(m) 1370(5) I V10 + v12]
1360(s)sh I V10 + Vll]
1320(m) 1310(3)
1300(3) 1300(m) 3 ring vibration
1290(s)
1270(8) 1250(9) I ”9 + V12]
1190(w) 1205(m) I “9 + V11]
1175(8)
1170(8) 1170(sh) “a ring breathing
1150(m) 1140(m) I ”12 + 650]
1140(9) I v12 + 8151
1130(m) 1120(m) I Vl] + 650]
1090(n) 1100(m) I v11 + 615]

 

Continued

 

 

Table TX. - Continued
Genuine
HT NnT Vibrational Assienment
Mode _

1070(n) 1080(vw) V5 ring deFormntion
1050(m) 1030(m) V7 rinp de‘ormation
1020(m) 1025(3) V8 ring de‘ormntion
1000(m) 1000(9) (1454-454) or 2(500)
950(m)

880(w) 890(vw) V10 C-H out-of—plane bend
860(3) [”12 + 350)

820(m) 830(5)

810(m) 7§O(w)

750(9) 760(8)

720(w) 720(u) V” ring de’ormnrfon
70H(m)

LIMI(\:) 0(M)(VJ)

631(w) 638(w)

608(5) 611(9) I “5 - V11]

522(9) 520(3) v12 out-oF-plane ring bend
499(w) 497(9)

447(3) 447(3) ”1] out-of-nlane rinn bend

409(sh) I “2 - V7]
387(m) 387(sh) I “3 - V10]
312nm 319m” I V7-”9]

 

Continued

 

 

Table IX. - Continued
Genuine
HT NaT Vibrational Assignment
Mode
249(9) 261(m)[b] I V9 - v11]
213(m)
200(w) 205(m) [ V10 - V9]
169(s) 191(5)

 

59

 

C8H8NAQ \V/*’\//“\//‘\

CO(C8”7N40)2.“20 W
N1(C8H7N40)1.8.H20 \aAA\xv~\/\//fi~‘vox\\\V//\\\f\\

 

db

 

 

\
CU((:8H7N40) (0H)
7N4”)2

 

. C"
7n( 8

 

Cr(C8H7N40)2(OH)o6H20 a.7KI7l\-I.\lAfVr7xP’\/\\\'\\\\_/\\NV

 

 

 

L___-l l 1 l 1 l l_

100 200 300 400 500 600 700
-1
cm
Figure 2 Far Infrared Spectra of S-p—Methoxyphenyltetrazole,
Sodium S-p-Methoxyphenyltetrazolate,and Various
Complexes of S-p-Methoxyphenyltetrazole

60

vmscwucou. H> oasmh ccmuwfi

WMM I w

 

H;_A3vomafi

_£~Asv0sflfl

_L~szmflmfl
.n.fiavohmm
Hn_Aevoqm~
”n.5evomom
H£_Aevo-~

_n_AsVom~H

 

 

Asvoowm
Amvowom Asvohom Amvooom Asvooom
AmvoOHm Amvoofim flavoonm .p_hmeomfim _L_Amvomfim Hn_amvomfim “evomom
.aafisvommm .cefimvommm .neawvomnm _n_nevommm .eeAmvoomm .neheeoemm
Amvowcm
Amvommm Amvomnm
o~m¢.Amcv~suu swam.~eam o~s.~e=u om:.m.aawz o~=.meou Hmz em
Hususoa cu ccoq Ecru wfiflzr
mcwwtwuacochxumxom vcm Horsz Cw mficnmuuoua7co£copoHLUIcam
mo mmeHCECL mchLc> vcm wumHCNCHquH>CmLCCMOH£U|Clm
Esfivcm .macswpumua>cwnccuoHLUICIm we Muuuocm vmumuwcH x mHan

61

woscwuccu

 

 

Asvmfima AeVoHNF Asvmomfi Amvommfi
Asvoomfi
Aevowmfl Acvommfl Aevcwwfl AmvommH Asvc~ma Aevmsmfi szmswfl
. mseanOOMH HL_AsvoomH flavoamfl AavoOMH
Aevcomfi flavo~m_ AEVOmmH Aevonmfi _neAsvomMH flavomma AmvoNMH
Amvmoqfl
AmVONqH Amvcmqfi AmvaQH Amvooem AmvaQH AmVONQH AmvmeH
AmVOOQH AmVCnQH Amvooqfi Amvomqfi Amvoqea AEVQOQH Amvomqfi
Aavohqfl flavowqfi szoocfi flavowQH Aavowqfl .pehavomqfi Amvmoqfl
flavommm szocmH flavofimfi havonH Aavmfima A3Vc~mH Aavmmmfl
Aevooms AmVOmmH Aevoomfl Amvohmfi szmomH Asvmomfi Amvommfl
Amvooofl vaoflcfi Amvooofi AmVoNoH Aevoflofi Amvofiofi AmVCOOH
Aavocmfi
Asvommfl
o~:q.fimcvmsue o~zm.~ecm cm:.me=e om:.w.fiefiz o~=.~ecu amz e:

 

em:Cfiucou I x ofinmh

consaucce

 

 

_n_fischm Amvoeo Amvcem Asvomo .pefischo Amvcea Aevocm

Aevomo. Aevowo Amvcmo Acvowa Asvowm Amvomm

Amvcac_ Aechofl Amvcmofi AmV0mofi Amvcfica Amvcocn Amvoccfi

Amvmfiofi

Aevcmofl AEVONOH AmvoNOH

AzVOmoH AEVONOH AsvomCH AEVONCH AEVOmoH Amvomoa

Anemooa

m Amvmmcfi

Amvomofi AmVCOHH Amvocfifi AmvooHH Amvooofl Amvoofifi Amvomoa

Aavomfifi AEVOMHH AmVOmHH Aevmmfifl havomfim Amvmmafi Aevomflfi

flavoefifl

“EVOOHH Amvosfle Amvmmfifi Acvcwen .LHAsvcomfi Asvcmfia AmVOOHH
szomHH

ommq.hmcv~sue cmzm.~ecw o~:.~eze cm:.m.mbwz o~=.~ecu Fez H:

 

wwscfiucco I

x mamas

63

wwacvucco

 

 

 

Asvome flavoqo Aevomo Aevoco Aaeomo Aevomo Amvomo
AmVONN AevoNs Amvmms AmvaN flavoms Amvomn Amvomu

Amvoen

Aevoms
AEVONN Amvoos flavoms Amemsh Aevoeh Amvoms Amvoqs
Aavoas Asvoow Aevoom Aavomu Amvooh Asvomh
Amvon Amvoqw Amvomm Amvomw Aevcmm Amvoqm Amvoqm
Amvcmw AmVme Aevocw Amvosw Aevcmw Amvomm Amvomm
_L_Asvowm Asvoom szcos szoom Hn_nmvmsm
:q.Amov~eue m.~ecN c~:.Ne=u. cum.m.fieez om:.~sou anz p:

ewscfiuzou I x mfinae

64

 

 

HLHAchmfi _;~Aquwm Amvomfi Amvosfl

AEVCCN .LHAmvmofi _i_fimveo~ Amvomfl szewfl

asvmmm mgefimvfimm havmflw
flaonN ~£_Asvmqm AmquN haveqm

Asvhew _;_Asvme~

AmvomN Aevmhm Amvmsm asvmum ,n_fievom~ AzmvwnN

Aevfiom Aeemom Amvcom ~s_fisvew~ Asvmmw Aqumw .a_haveo~

AEVOmm Asvmmm Aevhmm _;Haev¢mm .neAavsmm Asvaum

AEVONm

“avosm Aevsmm Acvosm szosn “semen Aaveom

Aevhcq Acvqsq Aquse Acvmsq Aevohq .Amvsoq Amvmmq

Amvscm AmVMHm Aevmom Amvsam Amvsfim “meson Anemom

Amvmmm

Acevooe .Leficvmmc AsymNQ Acmvmmo Anmvmfio

cmgq.fl;ovueuu nmem.mecs om:.msae c~x.x.fisrx owm.mpcu Hmz H:

emacwuccu .x «Hams

65

{1

 

 

Table XI. Infrared Spectra of S-n-Chloronhenyltetrazole
and Sodium S-n-Chloronhenyltetrazo]ate with
Band Assignments
Genuine
HT NaT Vibrational Assienment
‘fode k
3570(s) I”1-+‘h1]
3420(9) “13 0-H stretch
3300 (m) [It]
3090(m) 3]50(s)[b] v1 rine c-v stretch

3060(m)

2800(m)

2750(m)[b]
2720(m)[b]
2630(m)[b]
2540(n)[b]
2270(m)[b]

1‘H)(w)[‘v]

1600(8)
1550(9)
1525(w)

1495(5)

3060(5)

7270(")IP]
193an)Ih]
1920(m)
1900(w)
1610(s)
1565(m)
1520(w)

1490(w)[b]

I”: + 1(00]
[N~I’ strwiteh]
[”2 + V31

[“3 4 V6]

[“2 4~ WI

[V2 + V5]

{V7 + V10]
[“8 + V10]
IV4 + V9]

[V9 + “10]

[V7 + V12]

 

a Units are in cm‘1

b Brackets indicate possibJe assiqnments

Continued

66

Table XI. - Continued

 

‘_ *g-

 

 

HT NaT Vibrational Assignment
Mode

1480(5) 1460(m) v2 ring deformation

1435(3) 1420(5) V6 C-H in-plane bend

1405(5) [“10 + “12]

1370(5) 1350(m) [”10 + “1n

1700(w) 1310(m) V3 ring vibration

1275(w) 1275(m)

1260(w)

1250(n) 1255(m) [”9 + V12]

1180(w) [”9 + V111

1160(5) 1150(w) ”4 ring vibration

1140(m) IV12 + 650]

1120(m) 1125(3) IV12 + 615]

1090(3) 1100(3) [”11 + 650]

1085(5) [”11 + 615]

1065(5) [“9 + ”366]

1050(8) 1050(m) VS ring deformation

1020(5) 1020(m) 07 ring deformation

1015(3) I2 v12]

1000(8) 1000(5) v8 ring deformation
980(3) 980(m) [“11 + V12]
960(m) 900(m) [“2 - v12]
875(s)[b] 900(w) v10 C-H out-of-plane

 

Continued

67

Table XI. - Continued

 

 

Genuine
HT NaT Vibrational Assignment
Mode

850(3) 850(9) [v12 + 368]

840(9) 840(6) ["12 + 321]

790(w) 760(5) [”2 - ”9]

740(9) 750(9) 'Ive - V91

730(5) 720(8) 09 ring deformation
680(3) 650(m) [V4 - V111

615(sh) [“5 - ”11]

505(3) 507(8) v12 (out of plane ring bends)
459(8) 467(5) U11 . (out of plane ring bend )
366(w) 368(m) _ [”5 -V9]

321(w) IV7 -V9]

296(w)[h] 294(m) [”8 -V91

258(sh) 256(m)[b] [“9 - V11]

215(w) 221(s)[b] [“9 - v12]

186(w) 186(5) [V10 - V9]

17o<s> 1300:) I680 - "12]

 

CHNCl

NaC7HaN4C1

C0(C7114N4C1)2'H20

Ni(C7H4N4C1)1 8'" 0

2

Cu(C7HI.NAC1)2°HZO

2n(C7H4N4C])2-%H20
Cr(C

7"4N4

Figure 3

68

 

 

 

4P

 

3 1 I I

 

l j l I

 

 

C1)2(0H) '41120

 

 

 

\4/‘
I l L I 1 l 4
l
g 1 L A _1 l 1
100 200 300 400 500 600 700

cm

Far Infrared Spectra of SQp-Chlorophenylf
tetrazole, Sodium S-p-chlorOphenyltetra-
zolate and various complexes of

S-p-chlorOphenyltetrazole

69

 

 

 

coauwuccu .x emctw ccccofi mom a w
Amvcomm
Hn_nnvoqmm
Anvocom
AnVQONN
Aevoqcm AschOm
Aevcoom
Aevooom AsvomOM
Atnvccam AsvoHam Atnvooam _£aasvoon _L_Anvooam szcmam
AchOONm Acnvccmm
.s.AnV03mm
Hn_anvoomm _L_Anvccem _n_AsVOmmm _t_asvommm Aevoqmm
envoqmm
“envooem Atnvoocm Agnvomcm AthOOQM asnvocom
cmzq.:c~eno menu emxm.msso o~:.w.aeaz o~=.~ecc ann a:

 

automofi Cu ocoq Eco» mfianr
mcmwvmusncucfisoexo: 6cm Mowsz aw oflcumkueuH>~cmncuofizu1clm
no moxoficfcu catwum> can .mumacnmuumuH>~conoucfinu1c1m

Eswch .6ficnmuuoufi>uco20ucfixuucnm ec cuuumCm noumuwcH me oflxce
r.

70

voacwuccu

 

Azoomna

 

Aevomma Aevomma Aevoana asvnhna
asvoooa asvooea Hn_aevoaca Revoama Aavoama Aavomna
_p_A2voqoa .naasvocea _a_asvomoa _n_aavomoa Anvomoa
flavomaa Anvoqoa
Aavomaa Aavowha Aavoaaa
Aavooma Aaoooma _n_anoo~ma
Aavooma Azoowwa Aavoowa
_n_asvo~oa Aavomma _n_aavo~oa _n_aavo~ma “zoomed Aavoama Anvoama
szonaa
Aavocafi
Aavoeam _n_aevceo~
AnvoeeN
.AnvoweN
o~z«.=o~auu «ecu o~=m.~a=u o~=.m.aaaz o~m.~eou sea a:

 

vwscaucoo n max «Hana

71

voDCHuccc

 

 

 

AavcoN_ Anvcoafi havooma asvcoma .tHAtVOONH Anvoamfl AanONH
Mn_asvmema Anvomaa Aschma _n_Aavmqma aeaasvcnma Asoonaa Aavmqma
Anvmwma flavoowa
_t_azocmma Aevmoma nevoama “sycama AevomNH Acvowma Aavoama
_n_AeVona AsvonH _n_aavonH AaVona AnvonH flavoana
Aavonna
Asymmma _p_A2VommH _£_A2Vo~ma Aaoouma Aavnmma
Aeneasma
Aevomma Anvooqa asnvommH “accoma Anvoona Anymoqa
Aevcaqa Amvomqa Anvoaqa Anvoaqa Anvoaea Anvcmqa Anvoaea
_n_aevomqa Anvmqea _n_A2VquH Anvomqa Anvmmqa anvomna Anvoeea
Andeaqa .

~n_aaV0nqa Anvowna AsVONnH Anvomefl .e_aevc~qa AnvcaqH
Anvoqu Anvoqu Aneocmn Anvnoqa Amvoaqa Anvnmqa Anvmmqa
o~:e.A=cv~euo «one o~=~.~eao o~:.w.aaaz o~:.~hcu Fez a:

unscauaou . HHx manna

72

vmscfiuccu

 

 

szmmo
_n_aevcem Hn_aavoem ”peasvoeo Aevoea _n_azvcma AEVOmm Anyone
Asvoeo
Hn_aevomm _p.asvonm Aevowo AEVONm flavomm Asvmnm
Anomaoa AanHoH Anvoaoa Anvoaoa AnvaoH AnvmaoH Anyone
AmvoaoH Aevomoa Anomaoa
_c_aevomoH Anvmeca Asvomoa havoeofi Anvoaoa AnvomoH
Anyone” AnvmmoH Anvomoa AnvomoH Anvomoa Anvomoa Anvmwoa
Agnvoaaa AnVoHcH Anvmwaa Anvoaaa

Annemaaa Anvonaa

Anvoqaa Anvoqaa Asvoqaa Anvoeaa Amvmmaa

Anvomaa Anvomfia .t.aevocaa AEVOmHH Asvomaa
_;aasvc~aa Aevoana AnVONHH AsvcoHH

Anvmxfifi Atvmwfifi

cwmq.amcvmene mean emmm.mese o~:.w.aeaz mm.msco enz em

 

emscaucou 1 box nanny

vmacfiucoo

 

73

 

Asvome Aevcmo .nHAavomo flavomo A3V0mo Aevoco havomo
Asvooc Asymme Aeooae “tonne Anyone havomo
Aevooe Anvmcn Anvm0a Anomaa AgnVAeVmON Anvoaa flavomo
Anvo~a Anomaa Atvmma Anvomn mgefievoqa Aevomn
_;n_asvown Anvoma Atnvmoa asvoma Anvoma Andean
Anvmwa Anvoma Anvoan Anvoon Amvomn Anvmma
Anvoow Anemox asnvmom Anvoam Anemow
_t_hevmaw Anvmaw anaaevomm Anvowm
Amvomw flavoew Amvmmw
Asvoqw flavomw Asvomw Aseomw _c_aeemqm Anyone AEVOmm
_n_aavomm _;_A3Voaw _n_asvoaw Asvoaw
.naasvmao Anvmam Aevmam .naaevooa Anemoo Anomao
omze.A:cvmeno Necm cmzm.~a=o o~=.m.aeaz o~:.~eoo enz a:

 

tbSCHUCCU I HHX

74

 

 

 

Agenda szama
Atvana _t_A2VamH Asoka“ Annveaa .nuanveaa
atvnoa
Aavmcm szaam Asymmm Asvmam RDHAnvaHN
_n_anvmmm Atvamm szcqm Anv~ea AanMN
Aavmam Anvnam _naazvoau MLHAnVcaN
.peaavmmm Aav~w~ Aavmmm
szaCM Atvoam Asvwcm Aachen havaom
Anvamm Atom“ Anvmmm Asvmmm Asymmm Aevmam
Aavcmm szcwm szomm Asvaqm
flavonm Atvmnm Asvcwm anafiaveam _n_atvnom szaqm
Anvomm
Amvmee Asymmq “semen Arvaeq Anvnqc Aquwq Amvnnq
Anvqmq Anvcmq at_Anvowq
Atnvmmn Aavaom Asvmoq Anvmmq H;_Anvooq Anvamq Anvome
an_iaennm an_anvsan AnneHNn
Aznvmae
cmmq.;c~eno “new omzm.me:e cum.m.~w a o~:.~ecu enz a:
vengeance I .Hax natty

Table XTTT.

75

a
Infrared Spectra of

5—p-Chlorobenzvltetrazolate

and Sodium S-n-Chlorobenzvltetrazo]ate

 

 

Genuine
HT NaT Vibrational Assignment
Mode
3660(sh)
3540(sh) [V1 1 V111h
3340(m) “13 o.“ stretch
3300(5)[b]
3120(w) 3100(s)[b] “1 rinn c—n stretch
3080(0) [V2 * 16001
2700(3) “14 [N—H stretch]
2600(3) [“2 + “4]
2540(s)[b] [“2 + “51
2500(9)
2480(5) Iv3 + v4]
2440(3)
2160(m)[b] 2140(w) I2“sI
1910(5) 1920(w) [“7 + “10}
1890(w) [“4 + “9]
1820(s)[b] 1800(w) I2 “10]
1770(w) [“5 + “9]
1640(3) o-n bend

 

:1 Units

are in cm"1

b Brackets indicate possible

assienments

Continued

Table XIII.

Continued

 

 

Genuine
HT NaT Vibrational Assienment
Mode
1630(5) Iva-tvlll
1580(m) 1590(m) [“9-tv10]
1.575(m) 15mm) [850 + “91
1530(w) [V5 + v11]
1495(3) 1495(5) [V7-Fvll]
1470(3) [VS-tvlll
1440(5) 1430(3) ‘Jz ring deformation
1410(s) 1420(3) V6 C-H in plane bend
1405(3) 1400(9) [2‘@]
1355 1320(w) [v10 + v11]
1330(w)
1310(u) 1310(w)
1290(m) 11280(m) V3 ring deformation
1260(m)
1245(m) 1240(w) [v9-+V12]
1205(9) 1210(9) [v9-tvlll
1180(w0 T1170(s) 4 ring breathing
.1150(m) [“12 + 650]
1135(s) [“12 + 615]
1130(5)
1110(9) 1125(9) [“11 + 650]

 

 

Continued

Table XTIT -

Continued

77

 

 

Genuine
HT NaT Vibrational Assienment
Mode
1085(3) 1090(9) [“11 + 615]
11150(s) l(l70(s) V5 ring deformation
1015(5) 1020(m) V7 ring deformation
{390(5) 11}15(S) V8 ring deformation
075(n) 980(w) [“11 + “12]
960(m)
940(3) 950(m) [02 - 012]
935(w)
915(3) 965(m) V10 C—H out of plane bend
850(5) 850(s)
835(3)
820(3)
805(9) 810(3)
795(3)
770(3) 780(9) [V2 - V9]
720(m) 740(sh) [“6 - V9]
690 7]J)(S) 09 ring deformation
680(m) 690(9) [04 + V11]
650(0) 640(m)
618(sh) [“5 - “11]
521(3) In] V12 out-of-plane ring bend

 

Continued

Table XIIT. - Continued

 

 

Genuine
HT NaT Vibrational Assipnment
Mode

486(9) 497(9)

437(8) 424(9) V11 out—of-plane ring bend
367(w)[b] I“5 - “9]
319(m) [“7 - “9]

307(m) 307(w) [“0 - “9]

285(m) 282(m)

233(w) 242(9) [“9 -“11]
217(9)[b]

196
174(s)[b] [“10 - “9]

157

 

79

 

 

 

 

 

 

 

 

 

 

 

C Y ‘
8170461 '
1 1 1 J 4 ’
W\
rC
N1 8H6N4C]
1 1 J 1 1 L
CO<("8”6N.’IC1)2.HZO
1 1 £ ‘ 5 J i
Ni(C8H6N4C1)l.8°Hzn
_L L l l l I I
Cu(C8H6N4C1)2°3020 ‘“
_‘_ 1 J 1 I ' .1.--
/W \"J
An(C8”6NéCJ )2
1 A 1 1 L 4
Cr(CBH6N4Cl)2(0H)-4H20
_L A ‘ l L L i
100 200 300 400 500 600 700
0 cm'1

Fiwure 4 Far Infrared Spectra of S-p-CblorobenzyItetrazole,
h Sodium 5-p-Chlorobenzyltetrasolate and Several Complexes

of S-p-Chlorobenzyltetrazole

80

vaCwuccu

.e_arvomcm

.eaaevcmam
Heianvoomm

.eHAnVOmmm

 

.5 nanny ecoeefi new I n

 

l) I.“

Aavooom

ArvomOM flavoecm Aevoeom

_e_anvocam

_e_anvocem Heianvmamm

.eaA3VOmmm _e_aevocmm _e_anvommm

fleecema
_e_anvooem
.eaanvooem

.e_anvooN~

 

o~x<.mo~sno

NecN o~:.~a=e o~:.m.aeaz

Anvoomm
AnvomwN
AnvomeN
“evoeom Asvomcm Anvomom
Aavo_am
Aavomam
_e_aevommm
_e_aevonmm _e_anoonem Aavomem
Anvcnmm .eaanvommm
o~:.~eoo 962 H:

 

snanom

HIEoneH cu cooq Eoum mafia:
mcmwvcusncuofisomxo: can Henna :« waoumuuoua>cwnccuoHcousin
ec wmxoficsou mscwum> can wueflcumuuwuakcmno0po”cousin
.maoumuuou~>cmzcoucfisuuolm we muuownm vmumumcu >Hx manna

m

8]

benefiuccu

 

Anvoema

Aevomma

asvcema Aevmema Asvoema Aevmema flavoema flavoema Anvoema

Aevooea Aevocea Asvooma Aevooma Aevocea He_asvomma Anvooma
Aevmmea

Aevoeea Aevoeea Aaoonea AEVOmeH

AEVOONH AEVOONH AEVOONH

havomaa

Aevooma szoowa me_aavooma

AEVONwH .eaaevomma

_e_AsVoNoH AevoHea _eiA2VCCmH _n_aavomea .eaaavcmoa _e_azvowaa .e_aavc~¢9

Aevomea flavomma

Aavocom

Aevomow

o~m¢.mo~ene were ch.~e=c o~=.w.asez o~=.~seo eez em

 

menswucou I >Hx mHLmH

82

menswuccu

 

 

Aevomaa Aavomaa Anvomaa

Atvceaa .e_aevcmna _raasvoeflfi Aevoeaa Anvoeaa

.LHAEVONHH Atvcman .eaasvoaaa _e_fitvoaaa _e_acvoaaa Acvoaaa Andeaaa
AEVONNH szomma szooma Ascoama AEVOHNH

Aevomma Aevomma Aevmewa

Aevcema Aevonma

flavomma

Heaaevooma havomma _e_aevmoma aspvoomfi _e.Asvc0mH _e_atvona Asoomma

AeVOWmH ArVCmmH flavoema Asvoema Aavomma AeVOmmH Anvoema

Aevccma AnVCBmH

Aevmwea Aevocqa AchHeH Amvomea nevcmea Anvcmea Anvooqa
Aevceea Anvmmea

Arvoeea Aevceea “recess Arvoeea Aevomea Anoomea Aevmmea

Aevmuma Acvoama szchH asvmmma flavoama Ardooma Aevoeea

o~m<.:c~euo NecN o~m.~e=e omm.m.aeaz o~=.~ecu 962 e:

 

cmscauccu I >Hx capes

 

 

 

‘111 nllr
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Aevcme Aevowe Aevowe szomo Aromas Aryans Anyone
Anyone
Asymmca Aevmmcr AEVCNOH Asvomoa Arvoaoa AnvoHcH Anvcaoa
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m Aevoeoa
AEVONOH asvmeoa AsvcaoH Aevmeoa AsymmoH Andeaca Amvcsca
AmoceOH AsymmoH AevomcH asvoeca Aavomoa Asymmoa
Areas—a ArvmmcH Anvooaa Aevocaa

ASVQNHH
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o~z<.momepo Necm c~=.~eso o~:.w.aeaz ~:.~eto are H:

 

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84

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3 Aromas Aromas szmas
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szamm asvemm Aavmem _eaazvmem _e_fizvmmm
Anevcxm As>vc~m
Aevome Arvome Aevcme Aavome Atvome Anveme Arvcmo
omme.:oNHnu when cmz.msso om:.m.aeaz o~:.~eoo Haz a:

 

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I.>Hx macaw

 

86

 

Asvoma Aevema Anomaa Anvnaa Anvmea
_e_asvmoa

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87

 

 

 

Table XV. Infrared Spectr: of S-o-Chlorophenyltetrazole
Sodium S-o—Chlorophenyltetrazolate with
Assignments

Genuine I
HT NaT Vibrational Assignment
Mode
3550(s){b] [“1 + “11]b

3450(w)

3450(8)[b] “13 O-H stretch
3250(m)[b]

3190(m)

3120(m) “1 ring C-H stretch

3050(3) 3050(m) [1600 + “2]

2990(8) [2(1500)]

1820(8)

2800(8) V14 [N-H stretch]

2700(s)[b] [“3 + “6]

2600(s)[b] [2 “3]

2400(s)[b]

2390(m)

2050(m) [“7 + “8]

2000(m) I2 “10]

1950(m) [“7 + “10]

8 Units are in cm"1
b Brackets indicate possible assignments Continued

88

Table XV. - Continued

 

 

_ Genuine
HT NaT Vibrational Assignment
Mode
l920(w)[b] l920(w)[b] [“8 + “10]
1850(m)[b] [“4 + “9]
1800(m)[b] 1800(w) I2 “10]
1750(m) [“5 + “9]
1700(m) [“8 + “9]
1650(m) 1650(m) [“4 + “11]
1590(3) 1590(m)[b] [“9 + “10]
1560(9) 1560(m)
1550(9) 850 + “9]
1540(8) [“5 + “11]
1490(9) 1500(m) [“7 4 “11]
1455(9) 1450(9) “2 ring deformation
1435(9) ‘6 C-H in-plane bend
1400(3) 1420(9) [2(700)]
1370(9) 1360(9) [“10 + “11]
1360(9) 1350(5)
1290(m) 1310(m)[b] “3 rine vibration
1280(w)
1270(m) [‘9 +‘fi21

 

Continued

89

 

 

Table XV. - Continued
Genuine
HT NaT Vibrational Assignment
Mode
1245(5) 1220(In) [“9 + “11]
1210(m)
1170(8) 11700“) v4 ring breathing
1160(3) 1160(3) (702 + 454)
1150(3) 1150(m) [“12 + 650]
1120(5) 1135(s) [“12 + 615]
1120(w)
1100(In) 1100(8) [“11 + 650]
1075(III) 1090(w) [“11 + 615]
1070(8) 1070(8) V5 ring deformation
1060(3)
1040(8) 1040(3) “7 ring deformation
1030(8)
1010(8) 1010(8) v8 ring deformation
990(8)
980(3) 9700a) [“11 + “12]
950(n) 9500!!) [“2 - “12]
940(8)

910(vw)[b]

 

Continued

90

 

 

Table XV. - Continued
Genuine
HT NaT Vibrational Assignment
Mode
880(9) 890(w) 010 I C-H out of plane band
850(m)
785(m)
780(3) 780(3) [”2 - “9]
750(9)
750(9) [“6 - “9]
740(8)
730(8)
710(8) 720(8) V9 ring deformation
700(m)
650(3) 650(9) [“4 - ‘11]
521(m) 494(n) ‘12 out-of-plane rinn bend
475(w) 478(8)
440(w) 453(3) “11 out-of-plnne rinI' bend
435(w) 435(3) [‘2 - ‘7]
332(8) 333(8)[b] [‘7 - \9]
259(m) 270(8)[b] [\5 - ‘11]
252(m)
223(w) I 9 - 12]
212(w)

 

Continued

91

 

 

Table XV. - Continued
Genuine
HT NaT Vibrational Assignment
\fode
206(w) 208(w) [“10 - “9]
193(w)[h]
169(9) 177(9) [600 “12]

 

92

 

 

 

 

 

 

 

 

 

 

c705n4c1

1 L 1 1 1 1 1

l l l 1 1 1 1
Co(C7n4N4c1)2.H20

1 l l 1 1 4 J
Ni(C7H4N4C1)1 8.n20

l J I n 1 l 1

+1 I 1 1' l I 1

Zn(C7H4N4c])2

1 1 l £- 1 1 I
Cr(C7"4"4C‘)2(0n)-4u20

J. l l J 1 l 114

100 200 300 400 500 600 700

FigureS Far Infrared Spectra of S-o-ChlorOphenyltetrazole,Sodium
S-oChlorOphenyltetrazolate and Various Complexes of
S-o-Chlorophenyltetrazole

Table XVT.

93

Raoults of the Normal Coordinate Analysis

Calculation for Sodium Tetrazolate.

32

 

 

 

 

 

 

Species Vibrational Observed Calculated
Modes Frenuency PchuenCy A__
A1 “1 3120 3125
“2 1455 1461
“3 1290 1243
“4 1161 1138
“5 1065 962
”1 V6 1445 1453
“7 1023 1063
“8 1015 1013
“9 702 730
92 “10 910 910
“11 454 456
v I."
A2 12 --- 537
aUnits are in cm"1

Table XVII.

94

Infrared Spectrum for Sodium Tetrazolate
Monohydrate32 with Assignmentsa.

 

 

 

Vibrational Observed Assignment
Frequency, cm
3300 O-H stretch
“1 3120 C-H stretch
2930 [“2 + “m
2370 [“2 + “10]
1785 “ “9
1685 “8 “9
1640 O-H bend
V2 1455 sym. ring deformation
v6 1445 C-H in-plane bend
V3 1290 sym. ring deformation
1210 “9 + “12(8)
V4 1161 sym. rinp breathing
1132 “o + “11
v5 1065 sym. ring deformation
v7 1()23 :Isynl. rilin (lvf()rm:ILioxI
vi) 1015 asym. rlnw, deformation
v10 910 C-H out—of-plane bond
V9 702 asym. ring deformation
660 1640-08
V11 454 out—of-plane ring bend

asym. with reopect to

(In axis
2

 

“12

is taken as the calculated value.

Electronic Absorption Spectra

 

The band maxima for the complexes are displayed in Tables
XVIII to XXV. In most cases, additional bands were found in the
near infrared region (4000—10000 cm_1). These bands are possibly
overtone or combination bands of infrared bands found in the
650-4000 cm.-1 region.

The data in Table XVIII indicated that substituted
5-phenyltetrazoles and S-benzyltetrazoles are similar in ligand
strength to 5-trifluoromethyltetrazole (25), tetrazole (32),
and other strong nitrogen donors (64,65).

Unlike hexaaquocopper(II) and copper(ii) perchlorate hexahydrate
which may have a slightly distorted octahedral structure, the
appearance of the 281g+ “A13 band (64,65) seems to suggest Jahn
Teller distortion.

Jonassen _£ 31. (25) have suggested the utility of the

3.

3
ratio of the energy of the A2,» 13? (F) transition in the nickel

2
complex to that of the 81p» 2A1, transition in the corresponding

copper(II) complex. Jonassen gt _1. (25) reported that their
energy ratio of 1:3 is intermediate between that for complexes
containing six ligands ($1.4) and that for complexes displaying
weak tetragonal distortion ($1.1). This ratio is also shallor
than that for complexes displaying strong tetragonal distortion

’\;
(~1.6). The value for the energy ratio of approximately 1.1 in

this study indicates that the copper(II) complexes only QXperionce

95

weak tetraponal distortion. This value of 1.1 is very similar to
that obtained for diaquo bis(dipyridyl)copper(II), and tris
(dipyridyl)copper(II) (64).

In Table XVIII, the band positions in the complexes for the
281px 281g transition are listed in order of increasing energy.
It is expected that the maximum error in these bands is 100 cm-
at the slowest scan rate on the Cary Model 14 spectrophotometer.
Therefore it seems reasonable to suggest the following order of
ligand strengths:

.. _ ' 1 - — l l =
5 p C1C6H4Ch2Ch4>5 p CH30C614CR4

5-C6H5Ch4>5-p-C1C6H4CN4>5-o-C1C6HACb4

Although the copper(II) complexes with 5-p-methoxyphenyl-
tetrazole is a hydroxo complex there is apparently little differ"
ence between the spectra of hydroxo(5-substituted tetrazolato)
COpper(II) and that of bis-(5-substituted tetrazolato)c0pper(11).
For example, the spectrum of bis(5-phenyltetrazolato)copper(II)
monohydrate and hydroxo(5-phenyltetrazolato)c0pper(II) are quite
similar as shown in Table XVIII.

2

2
It should be stressed that the B1p+ Hg was not observed
in this work nor in that by Carber gt 1. (32).

An examination of Table XIX reveals that 5-o-chlorophenyl-
tetrazole is a stronger ligand than dimethylsulfoxide and dimethyl-
formamide, but it is slightly weaker than pyridine as evidenced

by a comparison of the band positions in the complex with those

_...~r

97

in the copper perchlorate hexahydrate in the same solvent.
Because of experimental difficulties in obtaining spectra that
are free of solvent peaks in the near infrared region
(4000-10000 cm-l), one cannot be certain wether the complexes
are tetragonal in solution. The reflectance spectra, however,
do suggest tetragonal symmetry.

The data in Table XX seem toindicate that the solid cobalt
complexes are octahedral because of similarities in the spectra
of the complexes with those of high spin 6—coordinate cobalt(II)
complexes and Co(Cl04)2°6H20. The band position of the shoulder
at approximately 19000 cm.1 was very difficult to determine in
this study.

The band positions in the solution Spectra listed in
Table XXI and associated molar absorptivities indicate octahedral
symmetry in solution. Based on the band positions in solution,
it appears that dimethylformamide, dimethylsulfoxide, and pyridine
are slightly stronger ligands than the tetrazoles.

In the case of the nickel(ll) complexes, it appears that
these complexes are octahedral as shown in Tables XXII and XXIII
by a comparison of the band positions and molar absorptivities
of these complexes with those of known octahedral complexes. A
comparison of the 3A2g + 3Tlg (F) band positions for all of the
nickel(II) complexes indicates that the S-p-chlorobenzyltetrazole

is the strongest ligand in the series and that 5-o-chlorophenyl—

tetrazole is again one of the weakest ligands. A ratio of 1.8

98

for the band positions of the JA2g + 3T1? (F) transition to the
3 V .

band Position for the 3A28 + ng (F) transition indicates
octahedral symmetry as well (64).

The chromium(III) complexes also appear to be octahedral as
shown in Tables XXV and XXVI by comparing the band positions and
molar absorptivities in the spectra of the complexes with those
of known octahedral complexes. From Table XXIV, it again appears
that S-p—chlorohenzyltetrazole is the strongest ligand in the
series due to the relative magnitudes of the band positions

+ 4

4
of the A?y T0 (F) band. Chromium(III) also appears to have

‘- )

octahedral symmetry in solution as shown in Table XXV.

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(B)
1 3 L 1
(C)
, __ i l 1
5000 10000 20000 25000
cm-1

Figure 6. Reflectance Spectra of (A) C0pper(II)
Perchlorate Hexahydrate (B) Bis(S-p~
ChlorOphenyltetrazolato) C0pper(II)
Monohydrate and (C) Bis(5-o-Chloro-
phenyltetrazolato) C0pper(II) Monohydrate

 

102

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107

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A-vco~ma Acmzcvo~=.w Haezoumuqxouauuounvaz
ooomm _ccsma. cocoa Awesomvc~=.m.aAezommuqmoofiuueumvaz
ROVCONNH Azmzmovcwx.w.erzoqmooaoneumvaz
afiflvoomsa Anzavc~:.w Haezoqmoofioneumvaz
ANHVocONN flavocsoa Asmzavc~=.w.aquoqmouauuaumvaz
comm_ _ooemfi_ cocoa Aeaacmvo~=.m.quzuqmooaouaumvfiz
Amevooosw Amvocsea Aznzmovo~me.mxecHovaz
.oNVoommN vaooaea Asvoosma Anzavcwmo.~xecHovaz
Aomvoomam Assessed havooema Asmravoame.~xqoauvaz
Hoeem~_ .Aamvomana. Homes. .mmmmH Awesomyewxo.wxecaovaz

. a . a a t , a .
Aavuaemf ~<m Apvaaem+ m<m uua+um<m vammem+ «(m wasochu

 

 

 

 

 

.moaonmuumh

uwuaueumnamun msoaump

we a mwxmaceou AHHvaxuwz m:u wcm mumuvmnmxum mumuoa:ouma aHHVmeuwz

uc wuuumCu cowusacm paw Has? Hersh.

e.e

oucmuumamum onu

we comwumnEOU <

.HHHxx prmH

112

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HHH>x «Hash w muocuoou mom m

 

 

 

 

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Amooooaa Amvoomaa Amroooa=.o.aquomzooumoaz
oomoa .oooaa_ ooeoa Aoaaomooao.m.axozomzooumoaz
oomam Aaavoooaa Azmzmoooa=.o.aAozoomoo-aououmoaz
Aomvoooaa Amavoomaa Aezovoa=.o.aaouoozoouauuoumvaz
oomma Hoooaaa ooqoa Aeaaomooam.a.anozoqmoouaouosmoaz
ooaam Aoooooaa AZmomoooax.a.aaozuozooomxoua-moaz
Amaooomaa Aooooaaa Aexooca=.m.axezoqzooomoouonmoaz
oomoa .ooeoa_ ooooa moaacmooam.m.aAozooxooomzu-csmoaz

umddddue
wahmzu ALqubmfomam Aevvahm+rm<m mafam< Auvumkm+cm< mcscpfiou

 

 

 

 

 

 

casewucou I

.HHHxx ”HSMH

113

Mutuommw um endow mo3 rem; accomumuco ca 0
no wocmuoema v

No mucmpwums u

.50 ooaoa one oomo .ooom .omam .omma um ocooe_oao3 mono; anacouaoo< o

 

 

 

a
HHH>x cases a muccucow mom a
oomea _ooaoao Aoaacmo oazo.:CaAozoaooozooauucumouo
oooma Hooaaaa Aoaacmooazo.zcaaozuezooaouosmvao
ooooa HoooaHH Aoaaomvoamo.mcaxemeqzoolmouo
ooaoa .ooaaao AoaHOmvcazo.=caaezoo:ooaoaeumvso.
.ooqaa. Aooacmooazo.Ascoaaqxocoooomzoucumoao
comma oooaa nos m+mnoooao
oomoa oomaa Aoo m+oamozvuo
oooam ooaea oooaa . ago aaoaoaooao
ooooa oooqaa AoaaomVoaeo.onoaoouo
Acvewbq + uu<c Ahyuaec + cm<c Ahvamhc + eu<q vcsoceou

 

 

 

 

mmecamuuofi wousumumesmlm wscmue> to nemxeasccu AHHchswEszu may cam
ouwsthcmxmm oumuefizusmm Aassvfiachpxe we mpuumcm Has: Homsz cam oucououmuua .>~xx oHan

114

 

mumsvazouaob

AHuwvesmsouno Acummoamuumuahcmzeamvmwn
oxouc»: nmv can ououvwnmxox oumuonuuom
AHHHVEDmaousu A<v mo muuumnm oucmuumawwm

.m muawmm

cemm 0003“ 0000a cocm

 

a g . d w .

Amv

 

 

A<v

 

 

115

 

 

 

 

 

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HHH>x «Heah m ouocuCOM mom «
Aoaoooooam Aaooooaoa WAhmtmoooaoo.:CaAozoozoocmze-enmoao
.ooeaa. mAemaceooazo.ICaAozeoooUCmooupumosu

m

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Auoooomm Aonvooaea Aaavoomaa AcmchCaze.=Caaezuozooaouo-moao
ooaoa _ooaaa. Aoaacmocaoo.=oaAozoooooaoaaumouo
aaoooomam Amaooooma Aoaoooooa AZmomovoaoo.aaeoaoouo
Auooomam Ammooomoa Aoaooooaa aezoooaao.maooaoopo
Aomoooomm Ammooooma Aomoooooa Aomroooaoo.maooaoouo
ooooa oooaa moaaomooazo.maooauvue
Acvofihq + a~<q Auvcpeq + «Nae Auvcmuq + umfiq . masocscu

 

 

 

 

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mo muuuoum newusaom new .Hasi Hansz d.oucmuuwmwmd osu uo ccwmsomsou < .axy odeeh

116

 

 

 

 

 

 

 

Aaaaooooaa Aemooooma aaooooaaa Aamomoooaoo.ooaxezomzooumouo
ooooa _oooaae moaacoVCaeo.ooaquemeoosmopo
Ammaooooam Aooooooea Amoooama mamamoocamo.=oaAozoamoqzooaouesmouo
oomaa Hooaoao moaacmooaeo.zoaaozeazoezooaououmouo

Anvaabq + emfV hhvuaeq + om<q Apvumaq + u~<q ~

cczoeaou

 

ooocaocco u .oxx mamas

Magnetic Moments

 

The magnetic moments of the various complexes are
listed in Table XXVI.

According to Barefield and Busch (69), high spin
6-coordinate, 5-coordinate and 4-coordinate cobalt(II)
complexes have magnetic moment values of 4.7-5.2,
4.2-4.6, and 4.2-4.8 respectively. Thus, only the pseudo-
octahedral 6-coordinate complexes can usually be identified
by use of magnetic moment data. The cobalt(II) complexes
of S-p-chlorophenyltetrazole, 5—o-chlorophenyltetrazole, and
S-p-chlorobenzyltetrazole appear to be octahedral or pseudo-
octahedral complexes. 0n the other hand, the cobalt(II)
complexes of S-phenyltetrazole and S—p-methoxyphenyltetrazole
may be either 5-coordinate or 4-coordinate and their magnetic
moments are very close to the spin only value. Magnetic
moments of these cobalt(II) complexes are very temperature
dependent.

Most of the cobalt(II) complexes have large values for
O, the Weiss constant. Figgis and Lewis (51) state that
large values of 0 indicate that the excited states lie far
enough from the ground state that they may be "thermally
occupied" at the temperature in question. In addition,
Cotton and Wilkinson (70) state that large values of O

can possibly be explained in terms of strong "interionic or

117

 

118

intermolecular interactions".

According to Barefield and Busch (69), high spin
6-coordinate, 5-coordinate, and 4-coordinate nickel(II)
complexes have magnetic moments of 3.0-3.3, 3.0-3.45, and
3.45-4.0 respectively.

The nickel(II) complexes of S-phenyltetrazole, 5—0-
chlorophenyltetrazole and S-p-chlorOphenyltetrazole may be
6-coordinate.

However, the nickel(II) complexes of S-p-methoxyphenyl-
tetrazole and S—p-chlorobenzyltetrazole may be A-coordinate.

The magnetic moments of the nickel(II) complexes are
very temperature dependent and the Weiss constanst are quite
large for these complexes.

The magnetic moments at 295° of 1.35 3.x. and 1.06 B.M.
for the cepper(II) complexes of S-phenyltetrazole and S-p-
methoxyphenyltetrazole are unusually low and may be due to
copper-copper interactions. Kato £3 31. (71) lave classified
c0pper-to-copper magnetic interactions as either direct
interactions or super-exchange interactions. Direct inter-
actions involve metal-metal bonding similar to that found in
copper(II) acetate monohydrate. Super exchange interactions
are more common when a ligand acts as a bridge between the
metal ions of 1.96 and 1.75. The magnetic moments of copper(II)
complexes of 5-o-chloropheny1tetrazole and S-p-chlorophenyl-

tetrazole are within the expected range of 1.7—2.2 for

 

119

copper(II) complexes. The magnetic moments of the copper(II)
complexes are very temperature dependent and the Veiss
constants are very large.

The magnetic moments of the chromium(III) complexes
agree with the expected value (51) of 3.8 -S.20. The
chromium(III) complex of S-p—mcthoxyphenyltetrazole has a
magnetic moment of 3.06 at 2950. This observed moment is
lower than expected and may be due to direct metal-metal
bonding or super exchange interaction by analogy with the

c0pper(II) complexes.

4 411nm? Aux-II- “-11

 

 

120

Table XXVI. Wannetic Moments a of the Cobalt(TT) Nickel(TT
’

Chromium(TII), and Copper(ll) Complexes of Various
S-Suhstituted Tetrazoles

 

 

 

 

(Iompound I 2930K 195°l-'. 77°K O (°K)
Co(5—p—ClC6H4CN4)2°H20 5.36 4.98 3.94 103
(Hw(5-C6H3CNA)2°H2O 4.09 3.91 3.01 113
Co(S-n-CH30C6H4CN4)2'H20 3.89 3.83 3.43 25
Co(S-o-ClC6HACN4)2-H20 4.99 4.57 3.89 130
Ni(H—C6HSCNA)].8-H20 3.07 2.90 2.43 80
Ni(5-o-C1C6H4CN4)1.8°H20 3.12 3.12 2.44 85
Ni(S-p—CIFOHACNZCN4)1.8'H20 3.60 3.57 2.52 ___
Cu(5-o-C1C6H4CN4)2°H20 1.96 1.89 1.42 100
Cu(5-n-41C6H4CN4)2-H20 1.75 1.56 .78 _
(M3(3-(4115CN4)((H1) 1.34 1.01 .79 300
Cu(S-n-cn3oc6n4CN4)(on) 1.06 1.39 .78 ___
Cu(3-p-ClChH4CH2CN4)2°3H20 _4__. 1.05 .73 200

 

Continued

121

Table XXVT. - Continued

 

 

Comnound 29S°K 195°K 77°F 0 (°V)
Cr(S-n-CH30C6H4CN4)20H-6HZO 3.06 3.15 3.04 0
Cr(S-p‘CJC6HACN4)20“'4H20 5.33 4.82 3,60 qu
Cr<5~C685CN4)20n-4H20 4.88 4.17 3.18 718
Cr(S-n-C1C6H4CN4)20H~4H20 3.91 3.77 3.12 75
(Ir('J-n-(I1(36H’.CHZCT~14)2011-41120 5.22 4.99 4.60 1530

 

in units nF Bohr Mnonetons

Electron Spin Resonance Spectra

 

The esr parameters for the copper(II) complexes are dis—
played in Table XXVII. The gavg values of 2.12 to 2.15
for these complexes compare very favorably with the gavg
values of copper(II) complexes with other nitrogen donors
(66). Likewise, the 8i and gl! values are similar to the
g|| and g1 values found for the copper(II) complexes of
pyridine, 4—cyanopyridine, and pentamethylenetatrazole (66).

Unfortunately in the absence of any accurate estimation
of 4L. the extent of tetragonal distortion is difficult to
estimate. However, the value of [gll - gll, which is a
measure of Splitting within the eg level is almost directly
proportional to the extent of diviation from octahedral
symmetry (67).

It is preposed that no signal is seen with the undiluted
copper(II) complexes of S-p-chlorophenyltetrazole and S~
phenyltetrazole due to spin-spin broadening. Similarly, the
broad unresolvable hand found for the copper(II) complex of
S-p-methoxyphenyltetrazole is possibly due to spin-spin
broadening.

The temperature dependence of the 95:1 (Zn:Cu) sample is

rather unusual and is not readily explainable.

The esr spectra of most of the cobalt(II) complexes are

122

123

very complex. It was impossible to calculate g values for
these complexes with the exception of bis(5-o-chlor0phenyl-
tetrazolato)cobalt(II) monohydrate. This complex shows
rather unusual behavior. Apparently the 3 value changes
with temperature. The g values of 2.55, 2.82, 2.87, and 3.01
at -4nO C,-100° c, ~13n° c, and -160° c. This increase in
p values with a decrease in temperature may be due to structural
changes which accompany changes in temperature.

The esr Spectra of the chromium(III) complexes are
displayed in Table XXVIII. The gavg value of 1.98 is similar
to that of other octahedral chromium(III) complexes (68).

The esr spectra of the nickel complexes consisted of

unresolved bands.

124

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125

 

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an HH.~ snoooa «zesmouonzo-aum
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126

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127

 

 

 

 

 

 

1000:]
333:1
1
60:1 1
/’*__’__,,,_
1 1
1
Neat P

 

 

 

 

Figure 10. ESD‘Spectra of 01s(5-o-Chloronhenvltetrazolato)
Copper(TT) “onohydrate at Various Zn:Cu Patios

128

 

30°

N

 

~40° to ~100°

 

 

~120°

 

~130°

 

 

 

 

Figure 11. ESR Spectra at Various Temperatures of
Bis(S-p-Chlorobenzyltetrazolato)
C0pper(II) Trihydrate Diluted.by a
Factor of 95:1 (Zn:Cu)

 

Cu(5‘0-C1C6114CN4)2'1120

 

Cu(5-p-C1C6H4CN4)2'U20

Cu(5-n-C1C6H4CH2CN4)2'3H20 h-————’/////\\\\//~/—*"’___

 

 

 

 

CU(5'C6”5CN4)(OH)

Cu(5-p-Cll3OC6114CN4) (on) J\r\
1

I.

 

 

 

 

 

Figure 12. A Comparison of the ESR Spectra
at -l60' of the Conser(II) Complexes
Diluted by 1000:1 (Zn:Cu)

130

coal um uumuuzcocox
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.MH ouauwm

 

 

 

 

10.

11.

10.
17.

18.

19.

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