SOME PROPERTIES OF

VANADIUM AND NIOBIUM PENTAFLUORIDES

by

RONALD GEORGE CAVELL

B.Sc, McGill University, 1958

A THESIS SUBMITTED I N P A R T I A L FULFILMENT OF

THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

i n t h e Department
of
CHEMISTRY

We a c c e p t t h i s t h e s i s as conforming t o the r e q u i r e d standard

THE UNIVERSITY OF B R I T I S H COLUMBIA

A P R I L i960
 In presenting this thesis in partial fulfilment of

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of B r i t i s h Columbia, I agree that the Library shall make

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agree that permission for extensive copying of this thesis

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Department of

The U n i v e r s i t y o f B r i t i s h Columbia,
V a n c o u v e r 8, C a n a d a .
 ABSTRACT

SOME PROPERTIES OF VANADIUM AND NIOBIUM PENTAFLUORIDES

The r e a c t i o n s o f v a r i o u s a m i n e s w i t h v a n a d i u m and

n i o b i u m p e n t a f l u o r i d e have been s t u d i e d . P y r i d i n e and

ammonia r e a c t e d w i t h v a n a d i u m n e n t a f l u o r i d e reducing

vanadium from t h e p e n t a v a l e n t to the t e t r a v a l e n t state

and forming monosolvated complexes of vanadium tetrafluoride.

The products i s o l a t e d were p y r i d i n e t e t r a f l u o r o v a n a d i u m I V ,

(Py)VF , l f and a m m i n o t e t r a f l u o r o v a n a d i u m I V , (NR\)VF^.

Ethylenediamine a l s o reduced vanadium p e n t a f l u o r i d e t o t h e

tetravalent s t a t e b u t f o r m e d a more h i g h l y solvated

denvative o f vanadium t e t r a f l u o r i d e . The p r o d u c t was

identified as t r i s ( e t h y l e n e d i a m i n e ) t e t r a f l u o r o v a n a d i u m IV

and has been f o r m u l a t e d as the o c t a h e d r a l comnlex

N i o b i u m p e n t a f l u o r i d e r e a c t e d w i t h ammonia t o f o r m

a 2:1 a d d u c t o f n i o b i u m p e n t a f l u o r i d e , d i a m m o n o p e n t a -

f l u o r o n i o b i u m V, ( N H ^ g N b F ^ . The p r o d u c t formed on r e a c t i o n

of ethylenediamine.. w i t h n i o b i u m p e n t a f l u o r i d e h a d the-

composition N b F ^ C e n ) ^ ^. I t has been c o n s i d e r e d as a

h i g h l y s o l v a t e d 1:1 a d d u c t ethylenediaminepentafluoroniobium

V. No r e d u c t i o n o f n i o b i u m h a s b e e n o b s e r v e d i n amine

reactions.

The infrared s p e c t r a and magnetic s u c e p t i b i l i t i e s of

the complexes have been measured and the d i s s o c i a t i o n

pressure o f d i a m m i n o p e n t a f l u o r o n i o b i u m V has been

determined. The s o l u b i l i t i e s and m e l t i n g p o i n t s of the

complexes were a l s o i n v e s t i g a t e d .
 The p e n t a f l u o r i d e s o f vanadium and niobium, i n

c o n t r a s t to the highest c h l o r i d e s o f the same metals,

are not s o l v o l y s e d by the amines studied here. This

common behaviour o f f l u o r i d e s , coupled w i t h an apparent

maximum c o o r d i n a t i o n number o f s i x f o r vanadium has been

used to e x p l a i n the r e d u c t i o n o f vanadium pentafluoride

by the amines.

The r e d u c t i o n o f vanadium o c c u r s because the a s s o c i a t i o n

of vanadium p e n t a f l u o r i d e i n the l i q u i d s t a t e has saturated

the c o o r d i n a t i o n number o f vanadium, so that any solvated

product formed by the amines has an unstable coordination

number which must be lowered. The f a c t that solvolysis,

which p r o v i d e s a method o f reducing the c o o r d i n a t i o n of

the c e n t r a l atom without reducing i t s valence s t a t e ,

can not occur w i t h f l u o r i d e s , r e q u i r e s t h a t the r e d u c t i o n i n

c o o r d i n a t i o n number o f vanadium must proceed through an

a l t e r n a t e mechanism w i t h concomitant r e d u c t i o n o f the

v a l e n c e of vanadium. This i n t e r p r e t a t i o n i s consistent

with the behaviour o f niobium p e n t a f l u o r i d e which forms

s o l v a t e d d e r i v a t i v e s i n which niobium has increased i t s

c o o r d i n a t i o n number to seven or e i g h t , the probable maximum

c o o r d i n a t i o n number o f niobium.

S t r u c t u r e s have been suggested f o r the products o f

the amine r e a c t i o n s . The p r o p e r t i e s o f the p y r i d i n e and

ammonia d e r i v a t i v e s of vanadium pentaf l u o r i d e , (Py)VF 4

and (NH-^VT^, plus the improbable c o o r d i n a t i o n o f f i v e

f o r vanadium i n the monomer suggests that the compounds are

polymers. -The most probable s t r u c t u r e i s a long c h a i n o f

VF .Base u n i t s l i n k e d by f l u o r i n e b r i d g e bonds such as

4

have been proposed to e x p l a i n a s s o c i a t i o n o f vanadium

pentaf l u o r i d e . The ethylenediamine d e r i v a t i v e of

vanadium pentaf l u o r i d e , (V(en-)J? , 4 i s probably a monomeric

compound, f o r t h e r e i s no need to p o s t u l a t e a s s o c i a t i o n

to i n c r e a s e the c o o r d i n a t i o n number o f vanadium to s i x .

The many complex ions formed by ethylenediamine suggest

t h a t i t i s reasonable to p o s t u l a t e the f o r m a t i o n o f the

(en)^*" 4
ion. T h i s i s the f i r s t hexacoordinate cationic

complex o f t e t r a v a l e n t vanadium, w i t h the e x c e p t i o n o f

vanadyl complexes, to be r e p o r t e d . The niobium

pentaf l u o r i d e complexes (NH^^NbF^, ( )Nbjp^ en m a v be

septacoordinate monomers, i s o s t r u c t u r a l w i t h i o d i n e

h e p t a f l u o r i d e , or o c t a c o o r d i n a t e f l u o r i n e bridged polymers.

The proposed s t r u c t u r e s are based o n l y on the few

q u a l i t a t i v e p r o p e r t i e s that are a v a i l a b l e f o r the

compounds. Complete s t r u c t u r e determinations are r e q u i r e d

f o r v e r i f i c a t i o n o f the s t r u c t u r e s proposed.

A n u c l e a r magnetic resonance study o f vanadium

p e n t a f l u o r i d e has y i e l d e d o n l y the F ^ 1
chemical shift

o f vanadium p e n t a f l u o r i d e of -335 ppm r e l a t i v e to

trifluoroacetic acid. The broad n u c l e a r resonance a b s o r p t i o n

obtained has been explained In terms of r a p i d f l u o r i n e

exchange o c c u r i n g i n c o n j u n c t i o n w i t h quadrupole broadening

due to the e l e c t r i c quadrupole moment of vanadium.

 ACKNOWLEDGEMENT

The w o r k d e s c r i b e d i n t h i s t h e s i s was done b e t w e e n

S e p t e m b e r 1958 a n d M a r c h i 9 6 0 u n d e r t h e d i r e c t i o n o f

D r . H. C. C l a r k , t o whom t h e a u t h o r w i s h e s t o express

h i s s i n c e r e thanks f o r the h e l p f u l advice and e n c o u r a g e m e n t

t h a t was a l w a y s available. The a u t h o r a l s o t h a n k s D r .

C. J . W i l l i s and t h e other members o f t h e I n o r g a n i c group

f o r much s t i m u l a t i n g d i s c u s s i o n .

The author i s g r a t e f u l t o the N a t i o n a l Research

Council f o r f i n a n c i a l assistance, i n t h e form of a

Studentship, during the period f r o m May 1959 t o A p r i l

I960.
 CONTENTS

CHAPTER PAGE

1. Introduction 1

2. Coordination and S t r u c t u r e o f T r a n s i t i o n M e t a l
Fluorides 10

3. Ammonia D e r i v a t i v e s o f Vanadium and Niobium

Pentafluorides 19

4. P y r i d i n e D e r i v a t i v e s o f Vanadium and Niobium

Pentafluorides : 30
5. Ethylenediamine D e r i v a t i v e s o f Vanadium and

Niobium P e n t a f l u o r i d e s 37

6. A Survey o f the Amine r e a c t i o n s 43

7. Nuclear Magnetic Resonance o f Vanadium

Pentaf l u o r i d e 53

8. Experimental

(i) General Techniques 57

(ii) A n a l y t i c a l Methods 62

(iii) F l u o r i n e Supply 66

(iv) The p r e p a r a t i o n o f Vanadium and Niobium

Pentafluorides 68
(v) The r e a c t i o n o f Vanadium P e n t a f l u o r i d e
w i t h Ammonia 71
(vi) The r e a c t i o n o f Niobium Pentaf l u o r i d e
with Ammonia 74
(vii) The r e a c t i o n o f Vanadium P e n t a f l u o r i d e
with P y r i d i n e 76
(viii) The r e a c t i o n o f Vanadium P e n t a f l u o r i d e
w i t h Ethylenediamine 79
(ix) The r e a c t i o n o f Niobium P e n t a f l u o r i d e
w i t h Ethylenediamine 81

(x) The Nuclear Magnetic Resonance Spectrum

o f Vanadium P e n t a f l u o r i d e 83

References 85
CHAPTER I ; INTRODUCTION

In 1946 r e l i a b l e commercial s u p p l i e s o f f l u o r i n e

became r e a d i l y a v a i l a b l e , thus s t i m u l a t i n g r e s e a r c h i n

a branch o f chemistry which had been neglected s i n c e

the e a r l y part o f the t w e n t i e t h c e n t u r y . Apart from

the p i o n e e r i n g s t u d i e s o f f l u o r i n e and i t s compounds

by Moissan and Ruff v e r y l i t t l e work had been done on

f l u o r i n e compounds, p a r t i c u l a r l y the f l u o r i d e s o f the

t r a n s i t i o n metals. Recent years have seen great

a c t i v i t y i n a l l branches o f f l u o r i n e chemistry; many

new compounds have been reported and the meagre and

c o n t r a d i c t o r y i n f o r m a t i o n a v a i l a b l e f o r many known

f l u o r i d e s has been supplemented by more r e l i a b l e d a t a .

F l u o r i d e s o f the t r a n s i t i o n metals have e x c i t e d much

interest i n the l a s t f i f t e e n years and w i l l continue

to do so i n the f u t u r e because o f t h e i r extremely

r e a c t i v e nature.

The s u b j e c t o f t h i s t h e s i s i s a study o f the

chemical behaviour o f vanadium p e n t a f l u o r i d e and a

related compound, niobium pentaf l u o r i d e , w i t h n i t r o g e n

c o n t a i n i n g , e l e c t r o n donor molecules.

Vanadium p e n t a f l u o r i d e was f i r s t reported by R u f f

and L i c k f e t t (1) to be a non-vo.latile orange s o l i d which

d i d not melt i n sealed tubes below 2 0 0 ° C This result

was not compatible w i t h the observed melting p o i n t s o f

other group VB p e n t a f l u o r I d e s , niobium and tantalum

p e n t a f l u o r i d e s which melt at 7&.9°C (3) and 91.5°C (2)

respectively. Recent work (4, 5) has shown that

vanadium p e n t a f l u o r i d e i s a c t u a l l y a white s o l i d which

melts i n sealed tubes to a pale straw coloured liquid

at 19.5°C, i n agreement with the expected increase i n

melting p o i n t with i n c r e a s i n g molecular weight w i t h i n

a subgroup. Vapor pressure measurements of vanadium

p e n t a f l u o r i d e (4, 5) give an e x t r a p o l a t e d b o i l i n g p o i n t

of 48.3°C which, when combined w i t h the l a t e n t heat o f

v a p o r i s a t i o n determined from the same d a t a , y i e l d s a

Trouton constant o f 33.1 cal/mole/deg. much higher

than the normal value o f 22 or 23 cal/mole/deg.

Many l i q u i d f l u o r i d e s have been found to have high

Trouton c o n s t a n t s , that i s they have a h i g h entropy o f

vaporisation. Abnormal Trouton c o n s t a n t s , are found i n

l i q u i d s w i t h h i g h v i s c o s i t i e s and r e l a t i v e l y h i g h b o i l i n g

p o i n t s , and are g e n e r a l l y i n d i c a t i v e of a s s o c i a t i o n of

some type i n the l i q u i d . These f l u o r i d e s are thought

to a s s o c i a t e through the f o r m a t i o n of f l u o r i n e b r i d g e

bonds ( 6 ) . Through a s s o c i a t i o n of t h i s type d i m e r i c or

polymeric s t r u c t u r e s o f the f l u o r i d e u n i t are formed i n

which the c e n t r a l atom achieves a higher c o o r d i n a t i o n

state. In t h i s manner vanadium p e n t a f l u o r i d e can form

 - 3 -

dimers (V F2 1 0 ) i n
which two o f t h e f l u o r i n e atoms a r e

situated inbetween t h e two vanadium atoms to form two

f l u o r i n e b r i d g e bonds. The s t r u c t u r e o f t h e r e s u l t i n g

dimer can be v i s u a l i z e d as two VF5 oetahedra j o i n e d by

a common edge. I n t h i s s t r u c t u r e each vanadium atom

i s hexacoordinate and presumably u t i l i z e s approximately

d sp- h y b r i d i s a t i o n w i t h a r e s u l t i n g o c t a h e d r a l con-
3

figuration. A s s o c i a t i o n to polymers, o f t h e type

( V F ^ ) , must a l s o be c o n s i d e r e d .
n Here t h e VF£ o c t a h e d r a l

u n i t s can be v i s u a l i z e d as s h a r i n g non-adjacent apices

so that t h e r e s u l t a n t s t r u c t u r e i s a long c h a i n polymer.

The vanadium atom i s a l s o hexacoordinate i n t h e polymeric

structure. Present evidence o n the nature o f the

a s s o c i a t i o n o f vanadium pentaf l u o r i d e however I s not

s u f f i c i e n t to I n d i c a t e whether dimers o r polymers a r e

formed.

The f l u o r i n e b r i d g e bond i s a t present p o s t u l a t e d

o n l y o n t h e b a s i s o f t h e q u a l i t a t i v e evidence o f a s s o c -

iation i n liquid fluorides. No q u a n t i t a t i v e c o n f i r m a t i o n

o f t h i s type o f bonding has been o b t a i n e d , thus i t s

s t a t u s i s s i m i l a r to that o f t h e hydrogen bond some

f o u r t y y e a r s ago. I t has proved to be u s e f u l i n

e x p l a i n i n g a s s o c i a t i o n phenomena without the presence

o f u n l i k e l y metal — metal bonds. Some v e r i f i c a t i o n o f

f l u o r i n e b r i d g i n g has been obtained i n s o l i d s where

X-ray s t u d i e s have shown f l u o r i n e atoms occupying

bridging positions (7). L i t t l e q u a n t i t a t i v e inform-

a t i o n Is a v a i l a b l e f o r l i q u i d s , i n f a c t the best

evidence f o r f l u o r i n e bonds i n l i q u i d f l u o r i d e s i s

obtained from the n u c l e a r magnetic resonance study

o f antimony p e n t a f l u o r i d e (8).

Antimony p e n t a f l u o r i d e i s a l i q u i d at room

temperatures with an extremely h i g h v i s c o s i t y ,

approaching that of g l y c e r o l . I t has a h i g h Trouton s 1

constant o f 2 5 . 9 cal/deg/mole. On t h i s qualitative

evidence alone i t i s probable t h a t antimony penta-

f l u o r i d e i s h i g h l y a s s o c i a t e d i n the l i q u i d state.

There Is no evidence to support the f o r m a t i o n o f

Sb - Sb bonds so presumably antimony p e n t a f l u o r i d e i s

a s s o c i a t e d through the f o r m a t i o n o f f l u o r i n e b r i d g e

bonds. The n u c l e a r magnetic resonance spectrum c o n s i s t s

o f t h r e e peaks w i t h r e l a t i v e i n t e n s i t i e s o f l s 2 : 2 s . The

s t r u c t u r e c o n s i s t e n t with the n u c l e a r magnetic resonance

spectrum and the h i g h v i s c o s i t y i s a long polymeric

c h a i n o f o c t a h e d r a l Sb'Fg groups j o i n e d at tvro o r t h o g o n a l

a p i c e s by f l u o r i n e b r i d g e s . There are then t h r e e groups

o f non e q u i v a l e n t f l u o r i n e atoms; one b r i d g e f l u o r i n e per

SbF^ u n i t ; two f l u o r i n e s t r a n s to the b r i d g e f l u o r i n e ,

and two f l u o r i n e s t r a n s to each o t h e r . Hoffman et. a l . ( 8 )

p o i n t out t h a t the b r i d g e bonds are c i s to each other

.(ie o r t h o g o n a l a p i c e s o f the o c t a h e d r a l u n i t a r e i n v o l v e d

i n t h e b r i d g e formation) i n order to u t i l i z e the most

f a v o u r a b l e bonding o r b i t a l s .

Many other f l u o r i d e s have been s t u d i e d w i t h n u c l e a r

magnetic resonance techniques (9) but i n no other

case can t h e r e s u l t s be d i r e c t l y i n t e r p r e t e d i n terms

of a f l u o r i n e - bridged structure. The r e s o l v e d s p e c t r a

have, i n many i n s t a n c e s , y i e l d e d much i n f o r m a t i o n as to

the s t r u c t u r e o f the f l u o r i d e monomer and t h e c o l l a p s e

of the r e s o l v e d s p e c t r a has been explained I n terms o f

fluorine bridging. The n u c l e a r resonance s p e c t r a o f

many f l u o r i d e s c o n s i s t s o f a broad, unresolved peak

which i s g e n e r a l l y a t t r i b u t e d to f i e l d averaging,

exchange phenomena. Broadening o f F 1 0 /

resonances I n

simple f l u o r i d e s i s g e n e r a l l y a t t r i b u t e d to exchange

I n v o l v i n g Intermediates associated v i a f l u o r i n e bridge

formation (9). R e s o l u t i o n o f exchange broadened peaks

has been accomplished i n s e v e r a l cases by c o o l i n g the

sample t o a temperature where t h e r a t e o f exchange i s

s u f f i c i e n t l y slow t o permit the observation o f the

n u c l e a r resonances i n the absence o f an averaging effect.

Because o f t h e h i g h melting p o i n t s o f many o f the

f l u o r i d e s studied, s u f f i c i e n t c o o l i n g could o n l y be

obtained u s i n g hydrocarbon s o l v e n t s w i t h extremely low

melting p o i n t s . The use o f s o l v e n t s i n s t u d i e s o f the

n u c l e a r resonance spectrum has i n d i c a t e d t h a t t h e simple

 - 6 -

d i s s o c i a t i o n process:

MF n MF _
n 1 +F*

does not occur because the s o l v e n t s a r e not f l u o r i n a t e d .

Approximate r a t e s t u d i e s o f the exchange (9) i n d i c a t e

that a second order process i s i n v o l v e d , thus supporting

the a s s o c i a t i v e mechanism i n p r e f e r e n c e to the above

d i s s o c i a t i o n mechanism! I t must a l s o be r e c o g n i z e d ,

however, that t r a n s f e r o f a f l u o r i d e can occur through

a s e l f - i o n i s i n g mechanism o f the type:

(MF ) n 2 ±=r MF*_ X * MF^ .

which i s thought t o occur i n many f l u o r i d e s .

Much evidence has been obtained from electrical

c o n d u c t i v i t y s t u d i e s o f f l u o r i d e s to support this

self-ionisation. An exchange process o f t h i s type

would a l s o broaden n u c l e a r resonance s i g n a l s and account

f o r a h i g h Trouton constant.

A s s o c i a t i o n and s e l f - d i s s o c i a t i o n are not mutually

exclusive processes. Energy requirements i n d i c a t e that

d i s s o c i a t i o n o f the type:

MF ± = ? MF * +F~
n n-1

which would account f o r the observed c o n d u c t i v i t i e s does

not o c c u r , hence s e l f - i o n i s a t i o n must i n v o l v e some form

o f a s s o c i a t i o n p r i o r to the f o r m a t i o n o f i o n s . Both

f l u o r i n e b r i d g e a s s o c i a t i o n and s e l f - d i s s o c i a t i o n could

be i n v o l v e d i n many f l u o r i d e s and i t i s not p o s s i b l e i n

 - 7 -

the l i g h t o f present knowledge to consider one process

to he more important than the other.

Vanadium p e n t a f l u o r i d e has been shown to have an

appreciable e l e c t r i c a l conductivity. Its s p e c i f i c

-4 -1 -1

c o n d u c t i v i t y (ksp = 2.3 x 10 ohm cm ) (4) i s

s l i g h t l y l e s s than that o f bromine t r i f l u o r i d e (10)

which has been shown to be a s e l f - i o n i z i n g solvent

(10, 11, 12). It has t h e r e f o r e been suggested (4) that

vanadium p e n t a f l u o r i d e s e l f - i o n i z e s according to the

equilibrium:

(VF ) ^VFj
5 2 +VFg

thus forming an acid-base solvent system. In t h i s

system-compounds c o n t a i n i n g the V F 4
+
i o n are d e f i n e d as

aci§s, those c o n t a i n i n g the VF^"" i o n as bases. The

d i s s o c i a t i o n of vanadium pentaf l u o r i d e probably involves

a p r e l i m i n a r y a s s o c i a t i o n i n t o f l u o r i n e bridge dimers

followed by t r a n s f e r o f the b r i d g i n g f l u o r i n e s from an

intermediate p o s i t i o n between two vanadium atoms onto one

of the vanadium atoms, thus producing the VF^* and VF^'ions.

Niobium and tantalum p e n t a f l u o r i d e s , on the basis

of t h e i r e l e c t r i c a l c o n d u c t i v i t i e s ( s p e c i f i c c o n d u c t i v i t i e s :

NbFcj - 1.63 x 10" 5

; TaF^ - 1.5 x i o " ohm" 5 1
c m ( I 3 ) ) ,also
- 1

appear to s e l f - i o n i z e i n a s i m i l a r manner to vanadium

pentafluoride:

(MF^) ^MFj2 + MF$

 - 8 -

The Trouton constants are higher than normal (NbF^ s

25.4; TaF^ = 25.9 cal/mole/deg ( 2 ) ) b u t not as high as

that f o r vanadium p e n t a f l u o r i d e , which suggests t h a t

niobium and tantalum p e n t a f l u o r i d e s may not be as

highly associated as vanadium p e n t a f l u o r i d e .

To prove the e x i s t e n c e o f acid-base solvent system

i n the group VB p e n t a f l u o r i d e s i t i s n e c e s s a r y to fulfil

three c r i t e r i a . First i t must be p o s s i b l e to o b t a i n

compounds c o n t a i n i n g the MF* and MF5 ions and to show

that these compounds are, at l e a s t , p a r t i a l l y ionic.

Second, the combination o f compounds c o n t a i n i n g t h e a c i d i c

(MF4) and b a s i c (MF5) ions must r e s u l t i n the f o r m a t i o n of

a s a l t and the s o l v e n t . T h i r d l y , i t must be possible

to perform n e u t r a l i z a t i o n r e a c t i o n s having d e f i n i t e

end-points -when e q u i v a l e n t amounts o f a c i d and base

have been mixed.

The o n l y evidence a v a i l a b l e i n support o f a

self-ionizing solvent system f o r the group VB

p e n t a f l u o r i d e s i s the i s o l a t i o n o f compounds presumably

containing the b a s i c (MF£) anion (14,15). No compounds

c o n t a i n i n g the a c i d i c (MF4) i o n are known. It i s

t h e r e f o r e not p o s s i b l e to conclude that the group VB

p e n t a f l u o r i d e s form new acid-base solvent systems on

the b a s i s o f e x i s t i n g evidence. L i t t l e i s yet known

about the r e l a t i v e Importance o f s e l f - i o n i z a t i o n and

f l u o r i n e b r i d g e a s s o c i a t i o n i n determining the properties

o f vanadium, niobium and tantalum p e n t a f l u o r i d e s , and

 - 9 -
c l e a r l y much more i n f o r m a t i o n i s required i n order

to o b t a i n a f u l l e r understanding o f t h e i r properties.
 - 10 -
CHAPTER 2: COORDINATION AND STRUCTURE OF TRANSITION

METAL FLUORIDES

The word c o o r d i n a t i o n has many meanings i n

s t r u c t u r a l chemistry which a r e e s s e n t i a l l y s i m i l a r

i n that they d e s c r i b e the s t e r e o c h e m i c a l relationships

between the s t r u c t u r a l u n i t s . A somewhat r e s t r i c t e d

d e f i n i t i o n , which w i l l s u f f i c e f o r a d i s c u s s i o n o f

the p r o p e r t i e s o f t r a n s i t i o n metal f l u o r i d e s , r e s u l t s

when c o o r d i n a t i o n i s considered as i t a p p l i e s to

c o o r d i n a t i o n complexes o f the type |cr(NH^)^jci^. In

a l l compounds In which c o o r d i n a t i o n o c c u r s , i t is

g e n e r a l l y considered that the r e s u l t i n g bonding

posesses both i o n i c and covalent c h a r a c t e r i s t i c s , and

so i t i s convenient to d i s c u s s the i n t e r p r e t a t i o n o f

c o o r d i n a t i o n number and s t r u c t u r e i n terms o f the s e t

o f simple o r hybridised o r b i t a l s used i n the covalent

c o n t r i b u t i o n to the bonding. The c o o r d i n a t i o n number

then f r e q u e n t l y i m p l i e s the u t i l i z a t i o n o f a c e r t a i n

set o f hybridised o r b i t a l s which a r e h i g h l y d i r e c t i o n a l

and posess a d e f i n i t e s t e r e o c h e m i c a l c o n f i g u r a t i o n so

t h a t the c o o r d i n a t i o n number can be r e l a t e d to the

structure.

In order t o understand more f u l l y the i n f l u e n c e

o f c o o r d i n a t i o n number on s t r u c t u r e and r e a c t i v i t y
 - II -

i t w i l l be n e c e s s a r y to consider the major f a c t o r s

i n f l u e n c i n g the c o o r d i n a t i o n s t a t e . For present

purposes t h i s may be done o n l y qualitatively.

The assumption that t h e r e i s some covalent

character i n the bonding i n v o l v e d i n complexes

r e q u i r e s that a s u f f i c i e n t number o f bonding o r b i t a l s

be a v a i l a b l e on the c e n t r a l atom f o r covalent bond

formation. In a d i s c u s s i o n o f complexes o f t h e

t r a n s i t i o n metals however, t h e r e are u s u a l l y more

o r b i t a l s a v a i l a b l e than r e q u i r e d f o r t h e formation,

of coordinate bonds. The formation of coordination

complexes o f the t r a n s i t i o n metals w i l l then be

i n f l u e n c e d p r i m a r i l y by the r e l a t i v e s i z e s o f the

ligand and the metal i n v o l v e d .

For a constant s i z e o f metal the s i z e o f the

l i g a n d w i l l be an important f a c t o r i n determining

the c o o r d i n a t i o n number o f the complex formed.

L i k e w i s e the s i z e o f the metal atom w i l l govern the

number o f l i g a n d s that can be aranged around i t .

I f the l i g a n d s are s m a l l , such as F , NH3 e t c . and

bonding hybrid o r b i t a l s are a v a i l a b l e , the s i z e o f

the metal atom w i l l govern the maximum number o f

l i g a n d s that can be bonded to the c e n t r a l metal

atom o r i o n . The maximum number o f l i g a n d s t h a t can

be attached Is the maximum c o o r d i n a t i o n number. The

 - 12 -

e f f e c t o f s i z e can be r e a d i l y observed i n a comparison

o f t r a n s i t i o n metals o f t h e f i r s t and second long

periods. Assuming t h a t maximum c o o r d i n a t i o n i s

achieved i n f l u o r o a n i o n s , which appears t o be g e n e r a l l y

t r u e from q u a l i t a t i v e evidence, t h e t r a n s i t i o n metals

of the f i r s t long p e r i o d , such as vanadium, chromium

managanese and i r o n , form the hexacoordinate ions

VFg, C r F ^ , FeF^3. N 0 heptafluoroanions a r e observed

i n the f i r s t long p e r i o d . In the second long period,

heptaf l u o r o a n i o n s a r e o f t e n formed, such as Z r F r , and

-2

NbFr; . The i n c r e a s e i n c o o r d i n a t i o n number from a

maximum o f s i x to a maximum o f seven or higher can be

a t t r i b u t e d to t h e i n c r e a s e i n s i z e o f the metal atom.

For example i n group VB, vanadium, which has a r a d i u s

o f 1 . 2 3 A ( 3 4 ) forms hexacoordinate f l u o r o a n i o n s ,

and niobium, whieh has an atomic r a d i u s o f 1 . 3 4 A ( 3 4 )

and forms h e p t a c o o r d i n a t e f l u o r o a n i o n s .

I f t h e assumption t h a t the f l u o r o a n i o n s exhibit

the maximum c o o r d i n a t i o n o f a metal i s c o r r e c t

(comparison w i t h other l i g a n d s shows t h a t higher

c o o r d i n a t i o n i s never o b t a i n e d ) , then i t i s apparent

from t h e above examples t h a t vanadium has a max-imum

c o o r d i n a t i o n number o f s i x whereas niobium can assume

a higher coordination state. The s i g n i f i c a n c e o f

t h i s maximum w i l l be demonstrated i n the r e s u l t s o f

 - 13 -
the present studies. I t i s apparent that where

a maximum s t a b l e c o o r d i n a t i o n s t a t e e x i s t s , any

s t r u c t u r e w i t h a higher c o o r d i n a t i o n s t a t e formed

i n a r e a c t i o n w i l l be unstable and tend to decompose

i n order that the c e n t r a l atom can r e v e r t t o i t s

maximum s t a b l e c o o r d i n a t i o n s t a t e . The products

o f a r e a c t i o n i n v o l v i n g an i n c r e a s e i n c o o r d i n a t i o n

w i l l be simple and s t r a i g h t f o r w a r d o n l y i f t h e

higher coordination state i s stable. I f the higher

coordination state i s unstable, the i n t e r m e d i a t e

formed w i l l tend t o r e v e r t to the lower coordinate

s t a t e by decomposition.

The s t r u c t u r e s o f polyatomic molecules and ions

are c l e a r l y determined by the c o o r d i n a t i o n number o f

the metal atom. The most important coordination

s t a t e s are f o u r and s i x . Of l e s s e r importance a r e

two, three, f i v e , seven and e i g h t . For a d i s c u s s i o n

o f t h e i n f l u e n c e o f c o o r d i n a t i o n on s t r u c t u r e and

r e a c t i v i t y f o r the group VB p e n t a f l u o r i d e s i t w i l l

be o f value to review b r i e f l y the higher coordination

s t a t e s , from f i v e t o eight inclusive.

Of the c o o r d i n a t i o n s t a t e s considered, penta-

c o o r d i n a t i o n i s the l e a s t common. A few molecules

are known t o be pentacoordinate i n the gaseous phase.

An example i s phosphorous p e n t a f l u o r i d e which has a

t r i g o n a l bipyramidal s t r u c t u r e , presumably u t i l i z i n g
 - 14- -

sp-^d o r b i t a l h y b r i d i z a t i o n . Although a t r i g o n a l

bipyramid i s the most l i k e l y s t r u c t u r e f o r a penta- s

2 2

coordinate molecule, square pyramids, i n v o l v i n g d sp

h y b r i d i z a t i o n are a l s o p o s s i b l e but no examples o f this

s t r u c t u r e are known. Presumably a t r i g o n a l bipyramidal

c o n f i g u r a t i o n o f atoms i s p r e f e r a b l e to a square planar

c o n f i g u r a t i o n because of the reduced r e p u l s i o n of

the l i g a n d s . Other examples o f p e n t a c o o r d i n a t e ,

t r i g o n a l bipyramidal molecules are NbCl^ and M0CI5 (17)

but i n general, very few pentacoordinate molecules are

known.

Pentacoordination has o n l y been v e r i f i e d in a

few molecules i n the vapor s t a t e , but no penta-

coordinate molecules have been found i n the liquid

or s o l i d states. The reason f o r the absence o f

pentacoordinate structures i n the condensed phases can

be a t t r i b u t e d to i n t e r m o l e c u l a r i n t e r a c t i o n leading to

an i n c r e a s e i n coordination. Thus i n the condensed

phases, where a s s o c i a t i o n i s l i k e l y (or i n s o l u t i o n

where solvent molecules can i n t e r a c t ;tfith the solute

increasing i t s coordination) a pentacoordinate structure

can become a hexacoordinate s t r u c t u r e . In the vapor

phase, where i n t e r a c t i o n i s g r e a t l y reduced, increase

in coordination w i l l be u n l i k e l y hence pentacoordinate

s t r u c t u r e s w i l l be found. The increase in stability

 - 15 -

accompanying t h e f o r m a t i o n of hexacoordinate

s t r u c t u r e s must he c o n s i d e r a b l e because many

examples o f a s s o c i a t i o n a r e f o u n d i n a p p a r e n t l y

pentacoordinate molecules. The group V p e n t a -

f l u o r i d e s such as VF^ n d SbF^,

a w h i c h have been

discussed p r e v i o u s l y , show a marked tendency t o

a s s o c i a t e through the formation of f l u o r i n e bridge

bonds and t h u s i n c r e a s e the c o o r d i n a t i o n s t a t e of

the c e n t r a l atom. A s e l f - d i s s o c i a t i o n p r o c e s s such

as t h a t p o s t u l a t e d f o r V F ^ i s a l s o a i d e d by t h e

increased s t a b i l i t y of the coordination states

produced. Thus VF^ can a c h i e v e more s t a b l e coordination

s t a t e s f o r vanadium by d i s s o c i a t i n g i n t o t h e t e t r a -
d-

coordinate vF^ i o n , w h i c h i s p r o b a b l y t e t r a h e d r a l ,

and the h e x a c o o r d i n a t e , o c t a h e d r a l VF^ i o n , Both

ions e x i s t i n c o o r d i n a t i o n states which are very

common and thus more s t a b l e t h a n t h e uncommon

pentacoordinate state.

Some examples o f p e n t a c o o r d i n a t l o n i n solids

have been s u g g e s t e d . F o r I n s t a n c e F o w l e s and P l e a s s

(19) suggested t h a t t h e complex, V C l ^ . 2 1 ^ 3 . c o u l d be

pentacoordinate. T h i s however was n o t s u p p o r t e d

by a s t r u c t u r e d e t e r m i n a t i o n and i n a l a t e r paper

( 2 0 ) they suggested the p o s s i b i l i t y o f d i m e n s a t i o n .

Complexes such as T i C l . N E t o a r e suggested by

) +
 - 16 -

G i l l e s p i e and Nyholm (17) as examples o f pentacoordination.

Muetterties (18) suggests t h a t complexes o f t h e group

I V f l u o r i d e s , eg. T i F ^ . C H ^ C N , a r e n o t pentacoordinate

as i n d i c a t e d by t h e i r stoichiometry but are rather

polymeric s t r u c t u r e s i n w h i c h t h e c e n t r a l atom i s h e x a -

coordinate. Thus p e n t a c o o r d i n a t i o n a p p e a r s t o be a n

u n l i k e l y c o o r d i n a t i o n s t a t e i n s o l i d and l i q u i d materials

and suggestions of pentacoordination must be a c c e p t e d

with reservation.

Hexacoordination i s t h e most common c o o r d i n a t i o n

state. Many e x a m p l e s o f h e x a c o o r d i n a t e s t r u c t u r e s a r e

known, f o r i n s t a n c e n e u t r a l m o l e c u l e s s u c h a s MoF^, W F ^ ,

SFg, S e
^ g e t c . , a n d c o m p l e x i o n s s u c h a s V F ^ , NbFg

Cr(M^)^ etc. The s t r u c t u r e i n a l l c a s e s i s b a s i c a l l y

octahedral utilizing d sp3 bonding h y b r i d s .

2
Slight

d i s t o r t i o n i s f o u n d i n some s t r u c t u r e s b e c a u s e o f s t e r i c

i n t e r f e r e n c e by t h e l i g a n d s o r i n t e r f e r e n c e o f non-bonding

e l e c t r o n s w i t h t h e bond o r b i t a l s , b u t a n o c t a h e d r a l

structure i s generally recognizable. The s t a b i l i t y o f

t h e h e x a c o o r d i n a t e s t a t e i s i n d i c a t e d by t h e l a c k o f any

tendency o f t h e h e x a c o o r d i n a t e f l u o r i d e s o f group VIB

(MoFg, W F r ) t o a s s o c i a t e i n t h e l i q u i d s t a t e (6). The

frequency of occurrence of hexacoordinate molecules also

supports the greater stability of hexacoordinate structures

over pentacoordinate or heptacoordina'te^structures.

 - 17 -
A few examples o f c o o r d i n a t i o n s t a t e s higher than

six have been v e r i f i e d . Higher c o o r d i n a t i o n s t a t e s

g e n e r a l l y are found i n complex anions such as

TaFrT, ZrF^ , Mo(CN)g etc.

3 4
( 1 7 ) . The o r b i t a l

h y b r i d i s a t i o n i s not f u l l y understood i n these compounds.

-3
The ZrFy i o n has a pentagonal bipyramid structure
involving d s p 3 3
hybndization. A face-centered trigonal-
4 2
prism s t r u c t u r e i n v o l v i n g d sp h y b r i d s has been suggested
for the heptacoordinate TaFr? =
anion. The octacoordinate
-4
anion M o ( C N ) o presumably has a square a n t i p r i s m s t r u c t u r e
5 3
formed by d p hybridisation. Few n e u t r a l molecules have

a c o o r d i n a t i o n number g r e a t e r than s i x , however i o d i n e

h e p t a f l u o r i d e i s an example o f a s e p t a c o o r d i n a t e molecule.

Hence s t e r i c c o n s i d e r a t i o n s i n d i c a t e t h a t coordination

s t a t e s o f seven or g r e a t e r w i l l be s t a b l e i f the c e n t r a l

atom o f t h e complex i s l a r g e (eg. i o d i n e ) o r i f the o v e r a l l

s i z e o f the complex i s expanded due to the presence o f

a charge on the complex.

In reviewing the v a r i o u s c o o r d i n a t i o n s t a t e s i t i s

apparent then t h a t many molecules, e x h i b i t i n g the unusual

pentacoordinate s t a t e are a c t u a l l y more h i g h l y coordinated

than t h e i r s t o i c h i o m e t r y would i n d i c a t e . A more common,

and presumably more s t a b l e , c o o r d i n a t i o n s t a t e i s then

formed by a s s o c i a t i o n o r some other means. Because o f

such i n t e r m o l e c u l a r i n t e r a c t i o n to produce higher coordination

s t a t e s , t h e r i g o r o u s assignment o f c o o r d i n a t i o n numbers
 - 18 -
i s always dependent on a complete s t r u c t u r e d e t e r m i n a t i o n .
 - 19 -

CHAPTER 3 : AMMONIA 'DERIVATIVES OF VANADIUM AMD

NIOBIUM PENTAFLUORIDES

Ammonia i s t h e s i m p l e s t of the nitrogen bases

considered. I t sability t o a c t as an e l e c t r o n p a i r donor

i s w e l l known. I t reacts w i t h simple electron pair acceptors

such as b o r o n t r i f l u o r i d e forming well defined adducts

(eg and i t a l s o f o r m s c o o r d i n a t e bonds with

t r a n s i t i o n metals having vacant d o r b i t a l s . Examples of

ammonia c o m p l e x e s f o r m e d w i t h t r a n s i t i o n m e t a l s a r e t h e

complex c a t i o n s such as [c (NH ) j

r 3 6
+ 3
.

Some t r a n s i t i o n m e t a l f l u o r i d e s a r e known t o f o r m

c o m p l e x compounds w i t h ammonia. F o r example, tungsten

hexafluoride g i v e s t h e p r o d u c t WF^.kNH^ i n l i q u i d ammonia

(16). The e x a c t n a t u r e o f t h i s compound, h o w e v e r , i s

not fully understood.

Ammonia, i n a d d i t i o n t o i t s e l e c t r o n d o n o r p r o p e r t i e s ,

i s also recognized as an a c i d - b a s e s o l v e n t system. It

i s thought t o s e l f - d i s s o c i a t e t o form a c i d i c and b a s i c

ionic species i n solutions

2NH3 NH.£ • NHg

Thus s c l v o l y s i s can occur i n l i q u i d ammonia i n a d d i t i o n

to the formation of donor-acceptor complexes. Compounds

w h i c h a r e s o l u b l e i n ammonia a r e o f t e n s o l v o l y z e d , e x i s t i n g

as h y p o t h e t i c a l a c i d s o r b a s e s i n t h e l i q u i d ammonia s y s t e m .

The relative stability o f ammonia w i t h f l u o r i d e s makes

it a good c h o i c e f o r the study of e l e c t r o n accepting

 - 20 -
p r o p e r t i e s o f compounds such as the t r a n s i t i o n metal

fluorides. Vanadium and niobium p e n t a f l u o r i d e s are

t h e o r e t i c a l l y capable of forming adducts because the

unoccupied d o r b i t a l s i n the metal atom can accept

e l e c t r o n s from a donor.

Vanadium p e n t a f l u o r i d e has been found to r e a c t

immediately with l i q u i d ammonia at -50°C to form a r e d d i s h -

brown s o l i d which was insoluble i n liquid ammonia.

Throughout the r e a c t i o n , m u l t i - c o l o u r e d s o l i d products

are produced which become r e d d i s h brown when complete

r e a c t i o n has o c c u r r e d . The reddish-brown solid loses

ammonia r e a d i l y u n t i l a pale grey-brown product i s o b t a i n e d .

The solid i s paramagnetic and X-ray powder photographs indi-

cate the presence of ammonium f l u o r i d e . On removal o f ammon-

ium f l u o r i d e by s u b l i m a t i o n the grey-brown s o l i d becomes a

darker brown and approximates to the composition VF^NH-^).

T h i s powdery dark brown s o l i d with the composition

VF (NH^) i s paramagnetic
4 with a magnetic moment of 2.14

Bohr magnetons, s l i g h t l y g r e a t e r than that expected f o r

t e t r a v a l e n t vanadium. A l l known t e t r a v a l e n t vanadium com-

pounds have magnetic moments c l o s e to the s p i n o n l y value

of 1.73 Bohr magnetons ( 2 6 ) . T i t r a t i o n o f a sample o f

the solid immediately upon d i s s o l v i n g in dilute sulphuric

acid s o l u t i o n i n d i c a t e s approximately 8% t r i v a l e n t vanadium

i s present i n a d d i t i o n to t e t r a v a l e n t vanadium which would

account f o r the s l i g h t l y h i g h value of the observed magnetic

moment.
 - 21 -

R e d u c t i o n o f vanadium pentaf l u o r i d e w i t h ammonia

to form p r i n c i p a l l y amminotetrafluorovanadium IV, (NH^vT^.,

i s strange i n view o f the tendency o f ammonia to solvolyze

t r a n s i t i o n metal h a l i d e s . Fowles and N i c h o l l s (24) have

found that l i q u i d ammonia s o l v o l y z e s vanadium t e t r a c h l o r i d e

producing a mixture o f amidobasic vanadium c h l o r i d e and

ammonium c h l o r i d e :

VC1 4 1- 6 N H - ^ V C I ( N H ) 3 + 3 N H G 1
3 2 4

S i m i l a r l y tungsten h e x a c h l o r i d e , a c c o r d i n g to Fowles and

Osborne ( 2 5 ) , i s s o l v o l y z e d hy l i q u i d ammonia, producing

a mixture o f ammoniated amidobasic tungsten chlorides

(WC1^(NH ), 2 2NH3 and V/C1 (NH ) ,

4 2 2 2NH3) and ammonium
chloride. S i m i l a r l y niobium p e n t a c h l o r i d e a c c o r d i n g to

Fowles and Pollard (22) i s solvolyzed:

NbCl^ 4- 4 N H 3 —^NbCl (NH ) 3 2 2 1- 2NH" C14

On the b a s i s o f these s t u d i e s i t would be reasonable to

expect s b l v o l y s i s o f vanadium pentaf l u o r i d e . This i s

not observed and the r e a c t i o n i n s t e a d a p p a r e n t l y i n v o l v e s

r e d u c t i o n and solvation.

R e d u c t i o n o f vanadium i n the r e a c t i o n w i t h ammonia

must be accompanied by an o x i d a t i o n o f some component.

The o x i d a t i o n product must be s u f f i c i e n t l y v o l a t i l e to

pass through a l i q u i d n i t r o g e n t r a p i n an evacuated system

because no o x i d a t i o n products v o l a t i l e or involatile,

were found i n the s o l i d product o r the v o l a t i l e m a t e r i a l s .

 - 22 -
It i s possible t h a t ammonia was o x i d i z e d t o n i t r o g e n

and the r e s u l t i n g hydrogen atoms used i n formation of

hydrogen f l u o r i d e which i n l i q u i d ammonia y i e l d s ammonium

fluoride. The e q u a t i o n f o r r e a c t i o n i s t h e n :

6VF^ + ll+NH 3 » 6VF (NH ) lf 3 • N 2 * 6NR4.F

One m o l e o f ammonium f l u o r i d e i s produced p e r mole o f

amminotetrafluorovanadium IV which i s i n agreement w i t h

the o b s e r v e d l o s s i n w e i g h t , o f a p p r o x i m a t e l y 20%, o n

r e m o v a l o f ammonium f l u o r i d e b y s u b l i m a t i o n .

A mechanism f o r t h e o x i d a t i o n r e a c t i o n c a n o n l y

t e n t a t i v e l y be s u g g e s t e d i n v i e w o f t h e f a c t t h a t t h e

o x i d a t i o n p r o d u c t i s unknown. I f ammonia was o x i d i z e d

to n i t r o g e n as suggested above, i t c o u l d occur through

the f o r m a t i o n o f f l u o r a m i n e and h y d r a z i n e and t h e i r

subsequent d e c o m p o s i t i o n t o n i t r o g e n a n d ammonium fluoride

according t o the equations:

6VF^ + 6NR" 3 +- 6 V F ( K H )l + 3 + 6F

6F + 6NH3 * 3M F 2 + 3NH4F

M F
2 + 2NH3 • »• N R \ 2 + KH^F

2NH F 2 + NgH^ *• N 2 * 2NHuF

Adding 6VF5 + 11+ NH3 6VFj (HH ) + 3 + N 2 * 6NB4.F

It i s o n l y p o s s i b l e t o s p e c u l a t e upon a mechanism until

more i s known o f t h e p r o d u c t s .

In c o n t r a s t t o t h e r e d u c t i o n o f vanadium pentafluoride,

niobium pentafluoride reacts w i t h l i q u i d ammonia t o f o r m

 - 23 -

a s t a b l e adduct, diamrainopentaf l u o r o n i o b i u m V (NH^) N b F ^

? 2

i n w h i c h no r e d u c t i o n o f n i o b i u m has occurred.

NhF ? 4-' 2NH —*-(NH ) NbF 2

The s o l i d i s diamagnetic i n d i c a t i n g pentavalent niobium.

T h e r e i s no ammonium f l u o r i d e p r e s e n t , according to

the X-ray.powder photograph, which e l i m i n a t e s t h e

possibility of the product being a m i x t u r e o f NbFi .(NH )

4 2

and NHi+F.

I t was m e n t i o n e d e a r l i e r that niobium pentachloride

was s o l v o l y s e d by l i q u i d ammonia ( 2 2 ) y i e l d i n g the

amido-basic c h l o r i d e , NbCl^NB^o.. Niobium pentaf l u o r i d e ,

i n contrast to the pentachloride i s not s o l v o l y s e d but

rather solvated. This l a c k o f s o l v o l y s i s c a n be a t t r i b u t e d

to the I n a b i l i t y of a NH 2 group t o r e p l a c e a F~ g r o u p .

Considering that the f i r s t step i n a solvolysis reaction

i s probably the formation of a s o l v a t e d intermediate, i t

i s more a c c u r a t e t o say t h a t b a s e - c a t a l y z e d elimination

of hydrogen f l u o r i d e from the s o l v a t e d intermediate does

not seem t o occur.

The i m p o s s i b i l i t y o f b a s e - c a t a l y z e d e l i m i n a t i o n of

hydrogen f l u o r i d e thus accounts f o r the formation of :

s o l v a t e d p r o d u c t s i n t h e r e a c t i o n s o f ammonia with

vanadium and n i o b i u m p e n t a f l u o r i d e s . The observation

t h a t vanadium p e n t a f l u o r i d e i s reduced while niobium

pentafluoride i s n o t and t h e d i f f e r e n c e i n t h e c o m p o s i t i o n
 - 2k -

of the r e a c t i o n products, ( N H ^ V F ^ and (NH^NbF^

c a n be e x p l a i n e d by t h e i n f l u e n c e o f c o o r d i n a t i o n on a

reaction. This w i l l be d i s c u s s e d later.

Amminotetrafluorovanadium I V , the brown powdery

s o l i d which remained a f t e r removal o f ammonium f l u o r i d e

b y s u b l i m a t i o n , was a slightly hygroscopic compound

which d i s s o l v e d q u i c k l y i n water to give green coloured

solutions. I t was not s o l u b l e i n s o l v e n t s such as

carbon t e t r a c h l o r i d e , ethanol (100$), benzene, ether,

nitrobenzene or p y r i d i n e . I t d i d not melt on heating

i n a sealed tube but r a t h e r decomposed t o a l u s t r o u s ,

powdery b l a c k solid a c c o m p a n i e d by e x t e n s i v e etching of

the tube.

Diamminopentafluoroniobium V was a brilliant yellow

diamagnetic s o l i d w h i c h was quite hygroscopic and

decomposed v i s i b l y in-moist air. I t was not soluble i n

liquid ammonia w h i c h suggests that t h e compound cannot

be formulated as NH£ [NbF^NHvJJ.

The observation that

s o l v o l y s i s by l i q u i d ammonia d o e s n o t a p p e a r t o occur

w i t h f l u o r i d e s would a l s o tend to support formulation as

a donor-acceptor adduct rather than formulation as an

ionic compound. Diamminopentafluoroniobium V, i n contrast

to amminotetrafluorovanadium I V and d i p y r i d i n e pentafluoro-

n i o b i u m V ( 1 5 ) , w h i c h decompose on h e a t i n g , appears to melt

at approximately 300° t o 3 1 0 ° C . M o d e r a t e a t t a c k of the

 - 25 -
g l a s s tube occurs at t h i s temperature which obscures the

melting p o i n t so t h i s r e s u l t i s not reliable.

The d i s s o c i a t i o n pressure o f diamminopentafluoroniobium

V has been determined. A p l o t o f l o g P v s . 1/T gives a straight

l i n e between 50° and 100°C which obeys the equation

log P(mm) = 5.62

10 - 1720

Assuming that the compound d i s s o c i a t e s completely a c c o r d i n g

to the equation:

( N H 3 ) 2 N W 5 ( S ) NbF 5 ( g ) • 2NH 3 ( g )

the heat o f d i s s o c i a t i o n , c a l c u l a t e d from the d i s s o c i a t i o n

pressure d a t a , i s &H = 7,870 cal/mole. Other thermodynamic

d a t a can be c a l c u l a t e d u s i n g standard r e l a t i o n s . The

r e s u l t s are t a b u l a t e d below along w i t h the thermodynamic

data f o r d i p y r i d i n e pentafluoroniobium (27). (Table I )

TABLE I

THERMO CHEMICAL DATA ON NIOBIUM PENTAFLUORIDE COMPLEXES

Compound &H Kp_ &F Ref

(cal7mole) 0 (cal/mole)
(NH ) NbF5
3 2 7,870 8.85xl0*"°(85 o c) 11,540 (85°C) 10.3(85°C) -
(Py) NbF52 22,940 2.84xlO"7(5o°C) 9,640 (50°C) 41.2(50°C)(27)

From the above thermochemical d a t a i t i s apparent

t h a t the ammonia complex i s much more s t a b l e than the

p y r i d i n e complex. This result Is to be expected because

ammonia i s a stronger donor than p y r i d i n e , due to the

r e d u c t i o n i n donor s t r e n g t h o f p y r i d i n e through delocalization

o f the e l e c t r o n s o f the lone p a i r . Ammonia i s a smaller

 - 26 -

molecule than p y r i d i n e hence the s t e r i c i n t e r f e r e n c e s are

expected to be much l e s s i n the ammonia complex. The
formation of X bonds does not appear to be an important f a c t o r
since the d e r i v a t i v e of p y r i d i n e , which i s capable of forming
ft bonds w i t h the metal, i s much l e s s s t a b l e than that of
ammonia.
The i n f r a r e d spectra o f amminotetrafluorovanadium IV
and diammino pentafluoroniobium V are very s i m i l a r and w i l l
be considered together. I t has been p o s s i b l e to assign
the frequencies using q u a l i t a t i v e arguments because of the
s i m p l i c i t y o f the s p e c t r a . The assignments are based on
the s p e c t r a l data f o r t r a n s i t i o n metal ammine complexes
(28, 2 9 ) . The absorption frequencies and assignments are
l i s t e d i n table I I .
TABLE I I
INFRARED FREQUENCIES OF AMMONIA DERIVATIVES
(NH )VF
3 4 (NH ) NbF5
3 2
ASSIGNMENT
3250 (s,b) 3100 - 3300 (s,b) asymmetric
N-H s t r e t c h
3100 (s,b) symmetric
2850 (sh) 2850 (sh) —
1650 (w,b) 1650 - 70 (w,b) degenerate NH 2 deformation
1425 (s) 1420 (s,b) symmetric NH 2 deformation
1075 (vw) 1055 (vw,b) -
980 (s) 937 (s,d) M - NH3 rock
913
800 (m,b) -
b -= broad, d = p a r t i a l l y resolved doublet, m - medium;
s B strong, sh - shoulder, vw - very weak, w - weak.
 - 27 -

The strong a b s o r p t i o n s i n the 3200 cm" 1

r e g i o n are

the N-H s t r e t c h i n g f r e q u e n c i e s . When r e s o l v e d , as i n the

case o f ( N H ) V F , t h e highest frequency i s assigned to the

3 4

asymmetric N-H s t r e t c h (which i s observed at 3414 cm" i n 1

gaseous ammonia) and t h e lower to the symmetric N-H stretch

(3170 c m - 1
i n gaseous ammonia). The assignment o f the other

frequencies i s less straightforward.

In the t r a n s i t i o n metal ammine complexes, the doubly

degenerate NH 2 deformation frequency i s l i t t l e changed

from t h e frequency o f the corresponding v i b r a t i o n i n gaseous

ammonia. In gaseous ammonia the value i s I 6 2 7 . 5 cm . In

twenty-eight ammines o f the f i r s t long p e r i o d t r a n s i t i o n

metals t h i s v i b r a t i o n appears between 1560 and "1650 cm" 1

(28, 29). T h i s a b s o r p t i o n frequency does not change mark-

e d l y on s u b s t i t u t i n g n e g a t i v e l i g a n d s f o r n e u t r a l ammonia

l i g a n d s , nor does i t change a p p r e c i a b l y w i t h the valence

s t a t e o r mass o f the metal atom. The a b s o r p t i o n p r o f i l e o f

the degenerate NH 2 deformation i s broad and o f moderate

intensity (29). It t h e r e f o r e i s reasonable to a s s i g n the

1650 cm~'i broad and r e l a t i v e l y weak a b s o r p t i o n s i n the

ammonia d e r i v a t i v e s to the degenerate NH 2 deformation

frequency.

The symmetric deformation frequency, which appears as

a doublet at 931 and 968 cm" 1

i n gaseous ammonia, was found

to range from 1150 to 1350 c m - 1

i n twenty-eight transition

metal ammines ( 2 8 , 2 9 ) . The a b s o r p t i o n p r o f i l e o f t h i s

 - 28 -

frequency i s g e n e r a l l y sharp and intense. T h i s frequency

i s extremely s e n s i t i v e to the o x i d a t i o n s t a t e o f the

c e n t r a l atom, g e n e r a l l y s h i f t i n g to higher wave numbers

w i t h i n c r e a s i n g v a l e n c e o f the c e n t r a l metal i o n . For a

constant valence o f the metal, exchange o f a n e u t r a l l i g a n d

for a negative ligand s h i f t s the frequency v e r y slightly

to lower wave numbers, but the e f f e c t i s s m a l l compared to

the s h i f t accompanying o x i d a t i o n . On t h i s evidence, the

1420 - 1425 peaks i n the ammonia d e r i v a t i v e s are assigned

to the symmetric NH 2 deformation frequency.

The remaining i n t e n s e bands o c c u r r i n g at 980 cm"-- i n1

(NH )VF3 4 and at 937 "90-3 in ( N B ^ M ^ are assigned to

the metal-ammonia r o c k i n g frequency. In the metal ammines

that have been s t u d i e d t h i s v i b r a t i o n o c c u r s between 650

and 950 cm -1
(28,29). T h i s frequency i s a l s o extremely

s e n s i t i v e to the nature and o x i d a t i o n s t a t e o f the c e n t r a l

metal i o n as would be expected, but i t i s not p o s s i b l e to

p r e d i c t any trends on the d a t a a v a i l a b l e . The a b s o r p t i o n

p r o f i l e o f the r o c k i n g v i b r a t i o n i s g e n e r a l l y broad and

intense. The assignment seems reasonable but the p o s i t i o n

o f the r o c k i n g f r e q u e n c i e s i s under study ( 2 8 ) . The reason

f o r the doublet i n the r o c k i n g frequency o f (NR" ) 3 2 NbF^ i s

not known. I t seems very u n l i k e l y that t h e r e would be

a M-NH^roeking frequency f o r each ammonia l i g a n d .

S e v e r a l bands are s t i l l unassigned. The source o f

the 2850 cm" 1

shoulder on the N-H stretching frequencies
 - 29 -

o f both d e r i v a t i v e s i s unknown. S i m i l a r l y the v e r y weak

bands at 1055 cm" 1

f o r (NH.3)VF and
4 1075 cm" 1
f o r (NH >
3 2

NbF^ are not identifiable. A medium i n t e n s i t y band at

800 c m -1
i n (NH^^NbFcj a l s o remains unassigned. It must

be emphasised that the assignments are based on q u a l i t a t i v e

d a t a obtained from o n l y a few compounds which are not

e s s e n t i a l l y o f the same type. The ammonia d e r i v a t i v e s o f

vanadium and niobium p e n t a f l u o r i d e s , f o r the b a s i s of compar-

i s o n , may be assumed to behave s i m i l a r l y to the transition

metal ammines, but t h i s assumption may not be justified.

It i s however the o n l y one that can be made with presently

available information.
 - 30 -

CHAPTER 4: P Y R I D I N E DERIVATIVES OF VANADIUM AND

NIOBIUM PENTAFLUORIDES

Pyridine i s a strong e l e c t r o n donor m o l e c u l e

and f o r m s many d o n o r - a c c e p t o r c o m p l e x e s . In contrast

t o ammonia t h e r e a r e no h y d r o g e n atoms bonded to

the n i t r o g e n so p y r i d i n e c a n be r e g a r d e d as a tertiary

amines, even simple a l i p h a t i c t e r t i a r y a m i n e s , and

is subject, t o l e s s s t e r i c interaction. The pyridine

ring system i s extremely s t a b l e . I t is stabilized

i n a s i m i l a r manner t o b e n z e n e and e x c e e d s b e n z e n e

in stability t h u s m a k i n g p y r i d i n e a good donor

molecule f o r the study of such r e a c t i v e a c c e p t o r s

as vanadium p e n t a f l u o r I d e . Many t r a n s i t i o n metal:

f l u o r i d e s a r e known t o ' f o r m c o m p l e x e s w i t b
pyridine.

Tungsten h e x a f l u o r i d e i s reported t o form a complex

with t h e f o r m u l a WF^.3Py ( 1 6 ) . N i o b i u m and tantalum

pentafluorides are reported t o form d i p y r i d i n e adducts

with t h e f o r m u l a e NbF^.2Py and TaF^.2Py (15).

P y r i d i n e , as a. l i q u i d or vapour, r e a c t s with

vanadium p e n t a f l u o r i d e t o form p y r i d i n e t e t r a f l u o r o -

v a n a d i u m I V , ( P y ) V F i , a d a r k b r o w n , powdery
+ solid.

The r e d u c t i o n o f v a n a d i u m p e n t a f l u o r i d e was confirmed

by t h e m a g n e t i c moment o f 1 . 6 7 B o h r magnetons found

f o r the s o l i d product. Tetravalent vanadium has one

unpaired e l e c t r o n and t h u s a m a g n e t i c moment o f 1 . 7 3

Bohr magnetons.
 - 31 -
The l o s s o f a f l u o r i n e atom i n t h e r e a c t i o n i s

puzzling. No f l u o r i n a t e d p y r i d i n e d e r i v a t i v e s were

found i n the v o l a t i l e f r a c t i o n s but a t r a c e o f an

u n i d e n t i f i a b l e r e a c t i v e f l u o r i d e was found along

w i t h p y r i d i n e removed from t h e r e a c t i o n v e s s e l .

T h i s s i t u a t i o n i s s i m i l a r t o t h a t encountered by

Wardlaw and Webb (30) i n t h e r e a c t i o n o f molybdenum

pentachloride with p y r i d i n e . The product obtained

by Wardlaw and Webb was a t e t r a v a l e n t molybdenum

compound w i t h the composition M0CI4.3PV. No t r a c e

o f the remaining c h l o r i n e was found and i t was

suggested that an i n d e t e r m i n a t e a d d i t i v e complex

was formed between 'free c h l o r i n e and p y r i d i n e and

was removed w i t h the excess p y r i d i n e . The p o s s i b i l i t y

of inadvertent h y d r o l y s i s obscuring the r e a c t i o n

can be excluded because Wardlaw and Webb were c a r e f u l

to ensure t h e dryness o f t h e i r reagents b e f o r e any

reaction.

The f o r m a t i o n o f an a d d i t i o n complex between

a f l u o r i n e atom and p y r i d i n e would e x p l a i n the

removal o f a f l u o r i n e atom, i n the r e a c t i o n w i t h

vanadium p e n t a f l u o r i d e , without t h e f o r m a t i o n o f

fluorinated pyridine derivatives. A f l u o r i n e atom

trapped i n such a complex would probably g i v e a

p o s i t i v e t e s t f o r f l u o r i d e i n the presence o f t r a c e s

of moisture.
 - 32 -
In a study o f the r e a c t i o n s o f vanadium

t e t r a c h l o r i d e w i t h a l i p h a t i c amines, Fowles and Pleass

(20) found t h a t at low amine c o n c e n t r a t i o n s , mono

and dimethylamines formed 1:1 a d d i t i o n compounds w i t h

vanadium t e t r a c h l o r i d e i n s o l u t i o n . On increasing

the amine c o n c e n t r a t i o n s , c h l o r i d e was found to he

r e p l a c e d by amine r e s i d u e s suggesting a base

c a t a l y s e d e l i m i n a t i o n o f hydrogen c h l o r i d e :

Both products are s o l v a t e d w i t h dimethylamine. No

r e d u c t i o n o f vanadium o c c u r s w i t h e i t h e r methylamine

or dimethylamine.

Trimethylamine, however, r e a c t s w i t h vanadium

t e t r a c h l o r i d e to form a t r i v a l e n t vanadium compound,

VCl .2NMe .
3 3 A c h l o r i n e atom was l o s t i n the r e a c t i o n

and, as i n the case o f the pyridine-MoCI^ reaction,

was never found. Base c a t a l y z e d e l i m i n a t i o n o f HC1

can not occur w i t h a t e r t i a r y amine, except through

breaking o f a C-H bond and the f o r m a t i o n o f unsaturated-

amines; t h e r e f o r e c h l o r i n e atoms are removed by some

obscure mechanism.

I f we c o n s i d e r p y r i d i n e to be a tertiary amine,

the s i m i l a r i t y o f t h e r e a c t i o n o f trimethylamine with

vanadium t e t r a c h l o r i d e and the r e a c t i o n o f p y r i d i n e

w i t h vanadium p e n t a f l u o r i d e becomes apparent. In

 - 33 -
both eases the covalent h a l i d e i s reduced to a

lower h a l i d e (with a more i o n i c c h a r a c t e r ) and

a halogen atom i s l o s t i n the process.

A reduction r e a c t i o n must be accompanied by

the o x i d a t i o n o f one of the r e a c t i o n components.

However i n the r e a c t i o n o f vanadium pentaf l u o r i d e

with pyridine, i n which vanadium has been reduced

to the t e t r a v a l e n t s t a t e , i t has not been p o s s i b l e

to i d e n t i f y the o x i d i s e d species. Therefore a

consideration of the r e a c t i o n mechanism must await

further study o f the r e a c t i o n p a r t i c u l a r l y w i t h

a view to i d e n t i f y i n g the o x i d a t i o n product.

The p y r i d i n e d e r i v a t i v e o f vanadium pentafluoride,

( P y ) V F , i s a dark-brown, powdery s o l i d which i s

4

i n s o l u b l e innon-reacting solvents. It dissoves i n

water g i v i n g green s o l u t i o n s which have an odour

of pyridine. On exposure to moist a i r , p y r i d i n e -

t e t r a f l u o r o v a n a d i u m IV q u i c k l y decomposed leaving

g r e e n i s h coloured residues. On heating i n a sealed

tube ( P y ) V F 4 d i d not melt, but rather decomposed

leaving s i m i l a r g r e e n i s h coloured residues which

appeared to be q u i t e inhomogeneous.

It i s u n l i k e l y that (Py)VF 4 would undergo the

simple d i s s o c i a t i o n s

(Py)VF 4 VF 4 f Py
 - 34 -

because vanadium t e t r a f l u o r i d e has been reported (1)

to d i s p r o p o r t i o n a t e to the t r i a n d p e n t a f l u o r i d e s :

VF 4 VF 3 + VF^

T h i s r e p o r t has never been v e r i f i e d . I f such a

d i s p r o p o r t i o n a t i o n occurs however the V F 4 produced

i n the d i s s o c i a t i o n would probably d i s p r o p o r t i o n a t e

to V F 3 and VF^, with VFej r e a c t i n g again with pyridine

and repeating the p r e p a r a t i o n o f (Py)VF4. The

g r e e n i s h c o l o u r s o f the decomposition products may

be due to vanadium t r i f l u o r i d e . The decomposition

o f (Py)VF4jbecause o f i t s complex nature, was not

investigated further.

There i s a marked d i f f e r e n c e between the

behaviour o f niobium p e n t a f l u o r i d e and vanadium

p e n t a f l u o r i d e with p y r i d i n e . C l a r k and Emeleus (15)

have reported that p y r i d i n e r e a c t s with niobium

p e n t a f l u o r i d e to form a 2 : 1 adduct, d i p y r i d i n e -

pentafluoroniobium V j (PY) NbF^.2 T h i s adduct i s

thus s i m i l a r to the adduct formed between ammonia

and niobium p e n t a f l u o r i d e , diammonopentafluoroniobium V ,

•which was d e s c r i b e d i n an e a r l i e r chapter. The p y r i d i n e

adduct i s l e s s s t a b l e than the ammonia adduct as

evidenced by the d i f f e r e n c e i n t h e i r d i s s o c i a t i o n

pressures. U n l i k e the ammonia adduct, the p y r i d i n e

adduct o f niobium p e n t a f l u o r i d e does not melt but

r a t h e r decomposes at 100°C. (15)

 - 35 -
F o w l e s and P l e a s s (21) have a l s o s t u d i e d t h e

r e a c t i o n s of niobium pentachloride w i t h various

aliphatic amines. The r e s u l t s a r e s i m i l a r to the

r e a c t i o n s o f vanadium t e t r a c h l o r i d e ( 2 0 ) . Mono

and dimethyl amines undergo b a s e - c a t a l y z e d elimination

of H C l thus s o l v o l y z i n g t h e c h l o r i d e w i t h amine

residues. An example i s t h e r e a c t i o n o f n i o b i u m

pentachloride with dimethylamines

NibCl^ 4. M e N H ^ [ N h C l . N H M e J - - ^ N b C l _ N M e
2 5 2 I ) 2 * HCl

NbClL..Me'2 + Me2NH-»JNbCl^NMe2 • M e ^ N b C ^ U H v ^ ) 2 + H
°l

a f u r t h e r s o l v a t i o n step occurs forming JNbCl (NMe)2*NHMe

3

but H C l i s n o t e l i m i n a t e d , p r o b a b l y because i t i s

sterically impossible t o b o n d t h r e e amine residues

to niobium.

This s o l v o l y s i s r e a c t i o n i s o n l y p o s s i b l e when

it i s possible to eliminate HCl f o l l o w i n g s o l v a t i o n .

A t e r t i a r y amine i s u n a b l e t o u n d e r g o s o l v o l y s i s because

t h e r e a r e no r e p l a c e a b l e h y d r o g e n s on t h e n i t r o g e n

atom. Reactions w i t h t e r t i a r y amines f o l l o w a

different course as evidenced by t h e r e d u c t i o n o f

vanadium t e t r a c h l o r i d e w i t h t r i m e t h y l a m i n e (20) and

the r e d u c t i o n o f vanadium p e n t a f l u o r i d e w i t h p y r i d i n e .

S i m i l a r l y niobium h a l i d e s react d i f f e r e n t l y with

t e r t i a r y amines as compared w i t h p r i m a r y and s e c o n d a r y

amines. Niobium p e n t a f l u o r i d e forms the d i p y r i d i n e

 - 36 -
adduct, niobium p e n t a c h l o r i d e forms no d e f i n i t e

product w i t h t r i m e t h y l a m i n e ( 2 1 ) .

P y r i d i n e r e a c t s w i t h vanadium and niobium

p e n t a f l u o r i d e s then to s o l v a t e the p e n t a f l u o r i d e s

as would be expected f o r a substance incapable o f

undergoing soIvolysis. The marked d i f f e r e n c e i n

f i n a l product, the a p p a r e n t l y pentacoordinate

t e t r a v a l e n t , vanadium compound.(Py)VF4„as a g a i n s t

the a p p a r e n t l y h e p t a c o o r d i n a t e , pentavalent niobium

compound ( P y ^ N b F i j can be a t t r i b u t e d to the e f f e c t

of the c o o r d i n a t i o n s t a t e on the r e a c t i o n . This

w i l l be more f u l l y d i s c u s s e d i n a l a t e r chapter.
 - 37 -
CHAPTER ETHYLENEDIAMINE DERIVATIVES OF VANADIUM

AND NIOBIUM PENTAFLUORIDES

Up to now o n l y the r e a c t i o n s o f u n i d e n t a t e donor

molecules, that i s molecules w i t h one donor group,

have been c o n s i d e r e d . Each c o o r d i n a t e bond formed

thus i n v o l v e s the attachment o f one molecule to the

metal atom. Ethylenediamine i s a b i d e n t a t e donor

molecule, that i s i t has two donating groups per

molecule, and thus can form two c o o r d i n a t e bonds

w i t h one molecule. Very s t a b l e complexes are t h e r e f o r e

formed on donating two e l e c t r o n p a i r s to the same

metal atom because the five-membered r i n g so formed

i s r e l a t i v e l y f r e e from s t r a i n . I t s small s i z e

combined w i t h the s t a b i l i t y o f the r e s u l t a n t five-

membered r i n g permits ethylenediamine to form complexes

i n which maximum covalency i s a t t a i n e d .

In a d d i t i o n to i t s c h e l a t i n g p r o p e r t i e s e t h y l e n e -

diamine i s a primary amine w i t h chemical p r o p e r t i e s

s i m i l a r to o t h e r a l i p h a t i c amines. I t was t h e r e f o r e

o f i n t e r e s t to i n v e s t i g a t e the r e a c t i o n s o f e t h y l e n e -

diamine w i t h vanadium and niobium p e n t a f l u o r i d e s .

Vanadium p e n t a f l u o r i d e r e a c t e d q u i c k l y w i t h

ethylenediamine to form a t e t r a v a l e n t vanadium compound

w i t h the composition VE4.3en. A magnetic suceptibility

measurement o f the paramagneticcompound confirmed the

 - 38 -

tetravalent s t a t e o f vanadium. The magnetic moment

of 2.0 Bohr magnetons i s s l i g h t l y higher than the

s p i n - o n l y value o f 1.73 Bohr magnetons expected f o r

t e t r a v a l e n t vanadium. As a l l known t e t r a v a l e n t

vanadium compounds have magnetic moments c l o s e to

the s p i n - o n l y value (26) i t seems u n l i k e l y t h a t

t h i s h i g h v a l u e i s due to s p i n - o r b i t c o u p l i n g or

other i n t e r a c t i o n s . The h i g h v a l u e i s probably due

to experimental e r r o r s i n the d e t e r m i n a t i o n o f

s u c e p t i b i l i t y or to the presence o f s m a l l amounts

of t r i v a l e n t vanadium. I t was not p o s s i b l e to

determine c h e m i c a l l y the o x i d a t i o n s t a t e o f the product

because i t was necessary to remove ethylenediamine

w i t h strong o x i d i s i n g c o n d i t i o n s before e s t i m a t i n g

vanadium.

The product o f the r e a c t i o n , t r i s (ethylenediamine)-'

t e t r a f luorovanadium IV, can be formulated as [V(en)3JF4

c o n t a i n i n g the o c t a h e d r a l complex i o n [ v ( e n ) ^ j . + 4

T h i s i s reasonable i n view o f recent s t u d i e s on t h e

r e a c t i o n s o f ethylenediamine w i t h vanadium chlorides.

Fowles and McGregor (23) r e p o r t t h a t ethylenediamine

r e a c t s w i t h vanadium t r i c h l o r i d e to y i e l d a similar

type o f compound, t r i s ( e t h y l e n e d i a m i n e ) t r i c h l o r o -

vanadium I I I :
 - 39

i n w h i c h the o c t a h e d r a l complex i o n is obtained.

Vanadium t e t r a c h l o r i d e however a p p a r e n t l y reacted with

ethylenediamine (23) b u t no d e f i n i t e p r o d u c t vras i s o l a t e d .

To e x p l a i n t h e d i f f e r e n t b e h a v i o u r - o f v a n a d i u m trichloride

and vanadium t e t r a c h l o r i d e w i t h e t h y l e n e d i a m i n e F o w l e s and

McGregor (23) s u g g e s t e d t h a t t h e more c o v a l e n t halide,

t h a t i s v a n a d i u m t e t r a c h l o r i d e , was s o l v o l y s e d by ethylene-

d i a m i n e w h e r e a s t h e i o n i c h a l i d e , V C l ^ , was s o l v a t e d by

ethylenediamine.

The f l u o r i d e s , o f c o u r s e , behave d i f f e r e n t l y f r o m

the c h l o r i d e s b u t we c a n t e n a t i v e l y a d v a n c e a similar

hypothesis to e x p l a i n the r e a c t i o n product. The covalent

f l u o r i d e , VFt>, i n c o n t r a s t t o the covalent chloride will

not be s o l v o l y s e d h o w e v e r b e c a u s e t h e r e are indications

in t h e ammonia and p y r i d i n e r e a c t i o n s t h a t s o l v o l y s i s of

f l u o r i d e s does not occur. Ethylenediamine w i l l react i n

the same manner a s p y r i d i n e a n d ammonia, r e d u c i n g VF5 t o

VFij., t h e "more i o n i c " f l u o r i d e . The more i o n i c f l u o r i d e

VF^. i s s o l v a t e d by e t h y l e n e d i a m i n e , i n t h e same manner

as t h e more i o n i c c h l o r i d e ^ V C l ^ was s o l v a t e d , t o f o r m t h e

h e x a c o o r d i n a t e jj/'(en) J*
3
If
i o n as the f l u o r i d e [v(en)^F _. l )

If the f o r m u l a t i o n of. t h e p r o d u c t a s j y C e n ^ F ^ i s

c o r r e c t then t h i s i s the f i r s t c a t i o n i c complex of

t e t r a v a l e n t vanadium, w i t h the exception of vanadyl complexes,

t o be r e p o r t e d . E t h y l e n e d i a m i n e f o r m s the t r i v a l e n t hexa-

coordinate complex, with vanadium trichloride

but no c o m p l e x e s w i t h v a n a d i u m t e t r a c h l o r i d e . Presumably
 - 40 -

the f o r m a t i o n o f a t e t r a p o s i t i v e complex i o n i s s t a b i l i z e d
by t h e h i g h e r charge d e n s i t y o f t h e f l u o r i d e i o n s compared
to c h l o r i d e i o n . Further studies are necessary to v e r i f y
the presence o f t h e complex i o n ^ J V C e n ) i * 1
"this product
but a t p r e s e n t none o f t h e observed p r o p e r t i e s c o n f l i c t
with t h i s formulation.

O n l y a few p r o p e r t i e s o f t h e complex compound, t r i s - .

(ethylenediamine) tetrafluorovanadium IV, a r e known. It i s
a brown powdery s o l i d i n s o l u b l e i n excess ethylenediamine,
and i n s o l u b l e i n p o l a r and n o n - p o l a r o r g a n i c s o l v e n t s such
as n i t r o b e n z e n e , e t h e r , a l c o h o l , p y r i d i n e , benzene and
carbon t e t r a c h l o r i d e . I t i s v e r y s o l u b l e i n w a t e r ,
presumably w i t h h y d r o l y s i s because t h e presence o f un-
occupied 3a o r b i t a l s on vanadium would make t h e complex
l a b i l e ( 3 1 ) . No e v i d e n c e however i s a v a i l a b l e t o support
h y d r o l y s i s so t h e complex i o n ^ ( e n ) ^ " 4
may be s t a b l e
i n aqueous s o l u t i o n . G e n e r a l l y , however, vanadium e x i s t s
i n aqueous s o l u t i o n as t h e complex oxygen c o n t a i n i n g i o n s :
VO*"*"; VO3, e t c . When heated i n a s e a l e d tube J]v(en)^ F 4

decomposes a t a p p r o x i m a t e l y l60°C. I t i s o f t e n found t h a t

compounds c o n t a i n i n g complex i o n s decompose when heated
r a t h e r t h a n show a d e f i n i t e m e l t i n g point.
Vanadium i s o b v i o u s l y reduced i n t h e r e a c t i o n w i t h
ethylenediamine j u s t as w i t h ammonia and p y r i d i n e . The
mechanism o f t h e r e a c t i o n i s not c l e a r and a g a i n a f l u o r i n e
 - 41 -

atom has been removed i n the r e a c t i o n without a t r a c e

appearing i n the v o l a t i l e 'materials or the s o l i d prdduct.

T h i s suggests that the r e a c t i o n does not i n v o l v e soIvolysis,

that i s e l i m i n a t i o n o f hydrogen f l u o r i d e , as would be

expected w i t h a primary amine and i n d i c a t e s a g a i n that

amines and ammonia do not s o l v o l y s e f l u o r i d e s . The reaction

probably i n v o l v e s s o l v a t i o n by ethylenediamine i n the

first step followed by r e d u c t i o n to t e t r a v a l e n t vanadium

because o f the u n s t a b l e nature o f the solvated product.

S o l v a t i o n o f the more i o n i c , t e t r a v a l e n t f l u o r i d e without

f u r t h e r r e d u c t i o n then o c c u r s to produce the complex

compound, lv(en)olF . 4

The i n f r a r e d spectrum o f F 4 was measured and

the peaks observed are l i s t e d i n the experimental s e c t i o n .

A rough comparison with the s p e c t r a o f ethylenediamine

complexes o f o t h e r t r a n s i t i o n metal ions r e p o r t e d by

Powell and Sheppard (32) shows many s i m i l a r i t i e s . The

s p e c t r a are complex as would be expected from the nature

o f the ethylenediamine molecule and as Powell and Sheppard

have not y e t p u b l i s h e d the assignments of t h e i r s p e c t r a

i t was not p o s s i b l e to a s s i g n the a b s o r p t i o n peaks o f

Niobium pentafluoride reacts with l i q u i d ethylene-

diamine forming a v i s c o u s brown syrup from which ethylenediamine

could o n l y be removed w i t h d i f f i c u l t y . A product o f

composition NbFcj(en) 6 was obtained a f t e r prolonged

1#
 - 42 -

heating under vacuum to remove ethylenediamine. Assuming

that the product is similar to other nitrogen base

derivatives, i t can be formulated as the 1:1 complex,

NbF^(en), which i s highly solvated with excess ethylene-

diamine.

Amines then do not solvolyse niobium pentafluoride

whereas according to Fowles and Pleass (21) niobium

pentachloride is solvolysed by aliphatic primary and

secondary amines. In this respect niobium pentafluoride

differs from the pentachloride. Ethylenediamine then

solvates niobium pentafluoride and because the solvated

product i s stable, s o l v a t i o n i s not followed by reduction

of niobium.

The product is then presumed to be a highly solvated

1:1 complex between niobium pentafluoride and the bidentate

nitrogen base, ethylenediamine. This formulation is in

agreement with the products formed by other nitrogen bases

and niobium pentafluoride, egi (NH^JgNbF^ and (Py) NbF^,

2 i n

which niobium has a minimum coordination of seven. The

solvated r e a c t i o n product, NbF^(en)-j_ g, was soluble in

water and presumably was hydrolysed. On heating in a sealed

tube the compound decomposed about 2hO°C y i e l d i n g an Inhomo-

geneous residue. Ethylenediamine was apparently liberated

and obscured the behaviour of the complex, (en)NbF^. No

further information could be obtained from the impure product.

 - 43 -

CHAPTER 6: A SURVEY OF THE AMINE REACTIONS

The r e a c t i o n s o f vanadium pentaf l u o r i d e with d i f f e r e n t

n i t r o g e n bases are s i m i l a r i n t h a t vanadium was always

reduced to the t e t r a v a l e n t s t a t e . The products t h a t were

obtained from the r e a c t i o n s are s o l v a t e d complexes o f

vanadium t e t r a f l u o r i d e . Ammonia and p y r i d i n e formed 1:1

complexes; amminotetraf luorovanadium IV, (NR^yVF^., and

p y r i d i n e t e t r a f l u o r o v a n a d i u m IV, ( P y ) V F 4 , whereas e t h y l e n e -

diamine formed the h i g h l y s o l v a t e d complex, t r i s ( e t h y l e n e -

diamine) t e t r a f l u o r o v a n a d i u m IV which has been formulated

as the complex compound £ v ( e n ) 3 J F 4 . Niobium pentaf l u o r i d e

formed a d d i t i o n complexes w i t h the same amines i n which

no r e d u c t i o n o f niobium o c c u r r e d . The s o l v a t e d products

obtained were diamminopentaf luoroniobium V, (NH-^NbF^,

and ethylenediaminepentafluoroniobium V, (en)NbF^. The

p y r i d i n e product, d i p y r i d i n e p e n t a f l u o r o n i o b i u m V, (Py)2NbF5,

has been p r e v i o u s l y r e p o r t e d (15).

It i s noteworthy t h a t vanadium and niobium penta-

f l u o r i d e s behave s i m i l a r l y with the amines i n t h a t o n l y

s o l v a t e d products were obtained and no evidence o f

s o l v o l y s i s by the amines was found. T h i s i s i n marked

c o n t r a s t with the behaviour o f the h i g h e s t c h l o r i d e s o f

vanadium and niobium which, according to Fowles and

co-workers (20 to 25 i n c . ) , are e x t e n s i v e l y s o l v o l y s e d by

ammonia and primary or secondary amines and are s o l v a t e d

o n l y by t e r t i a r y amines which are i n c a p a b l e of solvolysis.

 - 44 -

Niobium pentaf l u o r i d e formed simple a d d i t i o n complexes

i n which the minimum c o o r d i n a t i o n o f niobium was increased

from f i v e to seven. Vanadium p e n t a f l u o r i d e , on r e a c t i o n

w i t h amines, formed s o l v a t e d products i n which, except f o r

the case o f [V(en)3JF4, the apparent c o o r d i n a t i o n number

o f vanadium remained at f i v e . The product o f the ethylene-

diamine r e a c t i o n i s an exception to the behaviour o f the

amines i n t h a t vanadium has apparently formed a hexa-

coordinate complex c a t i o n .

It was i n d i c a t e d i n an e a r l i e r chapter t h a t penta-

coordinate s t r u c t u r e s , a r e extremely r a r e , e s p e c i a l l y i n

the l i q u i d and solid states. In view o f t h i s and because

o f the a s s o c i a t i o n t h a t has been p o s t u l a t e d for liquid

vanadium p e n t a f l u o r i d e i t i s therefore u n l i k e l y that the

compounds (Py)VF4 and (NR"3)VF4 are pentacoordinate,

monomelic complexes. Muetterties (18) has suggested that

the 1:1 amine complexes o f the group IV t e t r a f l u o r i d e s ,

which are i n s o l u b l e , non-melting s o l i d s , are probably

polymers. Because o f the known tendency o f simple f l u o r i d e s

to a s s o c i a t e , presumably by f o r m a t i o n of f l u o r i n e bridge

bonds, M u e t t e r t i e s a l s o suggested that the most l i k e l y mode

o f polymerisation o f the 1:1 complexes was f l u o r i n e bridge

bond f o r m a t i o n . I t seems reasonable to suggest therefore,

t h a t the 1:1 amine complexes formed from vanadium pentafluoride,

namely ( P y ) V F 4 and (NH/pVP^., which are a l s o i n s o l u b l e i n

 - 45 -

common s o l v e n t s and have no d e f i n i t e melting p o i n t s , a r e

a l s o f l u o r i n e bridged polymers. Through a s s o c i a t i o n o f

t h i s t y p e , vanadium then would be hexacoordinate r a t h e r

than p e n t a c o o r d i n a t e . Thus vanadium p e n t a f l u o r i d e , i n

which vanadium i s thought to be hexacoordinate through

the f o r m a t i o n o f f l u o r i n e b r i d g e s , r e a c t s w i t h amines to

form complexes i n which vanadium i s also hexacoordinate,

e i t h e r i n a monomeric complex such as j^V(en)3JF o r through 4

the f o r m a t i o n o f f l u o r i n e bridged polymers proposed f o r

(NH )VF4 and (Py)VF4.

3 There i s a p p a r e n t l y no net change

i n the c o o r d i n a t i o n o f vanadium on r e a c t i o n o f vanadium

p e n t a f l u o r i d e w i t h amines which i s i n agreement w i t h

the p r o p o s a l t h a t the maximum c o o r d i n a t i o n number o f

vanadium i s s i x as suggested i n an e a r l i e r chapter.

Niobium p e n t a f l u o r i d e forms the complexes (NH^^NbF^,

( P y ) N b F ^ and (en)NbF^ i n which t h e minimum c o o r d i n a t i o n

2

number o f niobium i s seven. An i n c r e a s e i n the maximum

c o o r d i n a t i o n number w i t h i n c r e a s i n g s i z e o f the metal atom

accounts f o r t h e f o r m a t i o n o f s e p t a c o o r d i n a t e complexes by

niobium whereas vanadium appears to have a maximum

c o o r d i n a t i o n number o f s i x .

Niobium p e n t a f l u o r i d e i s thought to be a s s o c i a t e d

through the f o r m a t i o n o f f l u o r i n e b r i d g e bonds i n the same

manner as vanadium p e n t a f l u o r i d e so that i n niobium penta-

f l u o r i d e , niobium would be hexacoordinate r a t h e r than i n

 - 46 -

the r e l a t i v e l y unknown p e n t a c o o r d i n a t e s t a t e . A l s o the

amine complexes o f niobium p e n t a f l u o r i d e may be f l u o r i n e

bridged polymers because i n g e n e r a l they do not have

d e f i n i t e melting p o i n t s . In t h i s r e s p e c t however, evidence

f o r polymerism i n the niobium p e n t a f l u o r i d e complexes i s

l e s s r e l i a b l e than that f o r the vanadium p e n t a f l u o r i d e

derivatives. I f the niobium p e n t a f l u o r i d e adducts are

f l u o r i n e bridged polymers, then niobium would be o c t a -

c o o r d i n a t e , -which i s probably the. h i g h e s t c o o r d i n a t i o n

number p o s s i b l e f o r niobium. C e r t a i n l y , no compounds

are known i n which the c o o r d i n a t i o n number o f niobium i s

g r e a t e r than e i g h t . The r e a c t i o n s o f amines w i t h vanadium

and niobium p e n t a f l u o r i d e s can then be considered t o

form complexes i n which the metal atom achieves t h e

h i g h e s t c o o r d i n a t i o n number possible.

I t has been suggested that a l l the amine d e r i v a t i v e s

o f niobium and vanadium p e n t a f l u o r i d e s , w i t h the e x c e p t i o n

o f the product polymers, probably through

the f o r m a t i o n o f f l u o r i n e b r i d g e bonds. The f o r m a t i o n o f

polymers through the f o r m a t i o n o f m e t a l - n i t r o g e n - m e t a l

b r i d g e s must not be overlooked f o r t h i s i s a p o s s i b i l i t y

i n ammonia and ethylenediamine complexes. The d i f f i c u l t y

of v i s u a l i z i n g such a bond i n t h e p y r i d i n e complexes

coupled w i t h the s i m i l a r i t y o f p y r i d i n e and ammonia complexes

suggests that M-N-M b r i d g e s areono.t formed and that the

 - 47 -

a l t e r n a t i v e o f f l u o r i n e b r i d g e bond f o r m a t i o n i s more

likely.

The s t r u c t u r e s o f the VF .Base compounds are probably

4

very s i m i l a r . The most l i k e l y s t r u c t u r e f o r both i s a

long c h a i n o f V-F-V b r i d g e bonds w i t h an o c t a h e d r a l con-

f i g u r a t i o n o f l i g a n d s about each vanadium atom. The

base molecules probably occupy p o s i t i o n on the c h a i n so

t h a t they are t r a n s to one another thus minimizing the

s t e r i c i n t e r a c t i o n s between base molecules. The structure

of the polymer would then be s i m i l a r to the s t r u c t u r e o f

the antimony p e n t a f l u o r i d e polymer (8) except that one

f l u o r i n e on each c e n t r a l atom has been r e p l a c e d by a

base molecule. The f o r m a t i o n o f such a s t r u c t u r e would

a l s o suggest that l i q u i d vanadium p e n t a f l u o r i d e may be

a long c h a i n polymer, s i m i l a r to antimony p e n t a f l u o r i d e .

The s t r u c t u r e o f the ethylenediamine complex o f VF 4

has been considered throughout as a simple hexacoordinate

complex compound i n which a l l t h r e e ethylenediamine l i g a n d s

are c o o r d i n a t e d to the same vanadium atom. This suggestion

may be an o v e r s i m p l i f i c a t i o n because the ethylenediamine

may c o o r d i n a t e to two d i f f e r e n t vanadium atoms forming

ethylenediamine b r i d g e s , hence t h i s amine complex may

a l s o be p o l y m e r i c . In view o f the known a b i l i t y o f

ethylenediamine to form monomer i c , hexacoordinate complex

i o n s , i t i s reasonable to assume the s i m p l e s t s t r u c t u r e ,

that o f the hexacoordinate ion £v(en)* " 4

 - 48 -

for the complex. I f t h i s i o n i s formed,, t h i s i s the

first c a t i o n i c complex of t e t r a v a l e n t vanadium, w i t h

the e x c e p t i o n o f the vanadyl complexes, to be r e p o r t e d .

The s t r u c t u r e s o f the niobium complexes i n c l u d e

many more p o s s i b i l i t i e s . They may be s e p t a c o o r d i n a t e

monomers i n which case the most l i k e l y s t r u c t u r e o f

the ammonia and p y r i d i n e complexes i s a pentagonal

bipyramid w i t h base molecules occupying p o s i t i o n s on

e i t h e r s i d e o f the pentagonal plane f o r a minimum o f

steric interference. I f the ethylenediamine complex

e x i s t s as a pentagonal bipyramid then the most l i k e l y

arrangement o f the n i t r o g e n atoms would c o n s i s t o f one

i n the pentagonal plane and one at an apex o f the

bipyramid. A l s o i n t h i s case the f o r m a t i o n o f e t h y l e n e -

diamine b r i d g e s must not be excluded, but i t i s u n l i k e l y .

The complexes may be f l u o r i n e bridged polymers, i n which

case niobium i s o c t a c o o r d i n a t e . A possible structure

would be a long c h a i n o f niobium - f l u o r i n e - niobium

b r i d g e bonds, as proposed f o r the vanadium polymers, with

an o c t a c o o r d i n a t e c o n f i g u r a t i o n o f l i g a n d s about the

niobium atom. The most probable o c t a c o o r d i n a t e c o n f i g u r a t i o n

i s a square a n t i p r i s m (17) although o t h e r s t r u c t u r e s must

not be excluded.

The s t r u c t u r e s that have been proposed are based o n l y

on the q u a l i t a t i v e i n f o r m a t i o n a v a i l a b l e f o r the compounds.

 - 49 -

A complete s t r u c t u r e d e t e r m i n a t i o n i s r e q u i r e d to v e r i f y

the proposed f l u o r i n e bridge bonds and to decide on the

t r u e c o o r d i n a t i o n number o f the metal atom.

The formation o f the products i s o l a t e d from t h e

r e a c t i o n can be explained by c o n s i d e r i n g t h e e f f e c t o f

a maximum c o o r d i n a t i o n number on t h e r e a c t i o n . The

i n i t i a l step i n t h e r e a c t i o n between an amine and t h e

p e n t a f l u o r i d e i s presumably the c o o r d i n a t i o n o f the

n i t r o g e n base to the metal atom, thus i n c r e a s i n g t h e

c o o r d i n a t i o n number o f t h e metal atom. I f the c o o r d i n a t i o n

s t a t e so formed i s s t a b l e , as i n the case o f niobium

p e n t a f l u o r i d e , then c o o r d i n a t i o n w i l l continue u n t i l the

maximum c o o r d i n a t i o n has been achieved. Thus niobium

p e n t a f l u o r i d e forms simple adducts w i t h amines i n which

the c o o r d i n a t i o n number o f niobium i s increased to a

minimum o f seven.

I f on the other hand the c o o r d i n a t i o n complex formed

by the i n i t i a l s o l v a t i o n o f the p e n t a f l u o r i d e i s unstable

because the maximum c o o r d i n a t i o n number o f t h e metal has

been exceeded, as w i t h vanadium p e n t a f l u o r i d e , then the

solvated complex w i l l decompose to a more s t a b l e c o o r d i n a t i o n

state. With vanadium pentaf l u o r i d e the f o r m a t i o n o f a

s t a b l e c o o r d i n a t i o n s t a t e i s accompanied by r e d u c t i o n o f

vanadium to the t e t r a v a l e n t s t a t e . I f s o l v o l y s i s o f the

f l u o r i d e s could occur, the c o o r d i n a t i o n number o f vanadium

 - 50 -
i n the s o l v a t e d intermediate could be decreased without

a r e d u c t i o n i n the v a l e n c e o f vanadium. However i t has

been observed that f l u o r i d e s a r e not s o l v o l y s e d by amines

so that s t a b i l i s a t i o n o f the c o o r d i n a t i o n s t a t e follows

a mechanism probably s i m i l a r t o that i n v o l v e d i n the

r e a c t i o n o f vanadium t e t r a c h l o r i d e w i t h trimethylamine

(20). Trimethylamine, w i t h no r e p l a c e a b l e hydrogens,

cannot undergo s o l v o l y s i s so that s t a b i l i s a t i o n o f t h e

coordination s t a t e was e f f e c t e d by the l o s s o f a c h l o r i n e

atom and r e d u c t i o n o f vanadium t o the t e r v a l e n t s t a t e .

VC1 4 f Me N — | y c i
3 4 • -Me^] »» VC'^NMe^ •+ [ c i ° ]

The formation o f the complex | V ( e n ) ^ j F , can be

4

a t t r i b u t e d t o the h i g h s o l v a t i n g power o f ethylenediamine

which s o l v a t e s the vanadium t e t r a f l u o r i d e produced by

the i n i t i a l r e d u c t i o n o f vanadium p e n t a f l u o r i d e with

ethylenediamine. In t h e i n i t i a l stages o f the r e a c t i o n ,

ethylenediamine probably resembles ammonia and p y r i d i n e .

It i s not p o s s i b l e w i t h the a v a i l a b l e i n f o r m a t i o n t o

propose a d e t a i l e d mechanism f o r t h e r e a c t i o n s o f t h e

p e n t a f l u o r i d e s w i t h amines. This i s e s p e c i a l l y true of

the vanadium p e n t a f l u o r i d e r e a c t i o n s where t h e o x i d i s e d

species i n t h e r e a c t i o n s have not been i d e n t i f i e d . The

r e a c t i o n s must be i n v e s t i g a t e d more f u l l y before any

mechanism can be suggested.

It has been noted that vanadium and niobium penta-

f l u o r i d e s are not s o l v o l y s e d by amines whereas the

 - 51 -
corresponding c h l o r i d e s a r e . The f a c t that amines w i t h

r e p l a c e a b l e hydrogens such asammonia and ethylenediamine

do not s o l v o l y s e the f l u o r i d e s suggests t h a t the d i f f e r e n c e

may be due to the d i f f e r e n c e i n the s t r e n g t h o f the metal-

halogen bond. T h i s d i f f e r e n c e i n energy need not be very

great f o r there are other energy terms i n v o l v e d i n the

r e a c t i o n , such as the l a t t i c e energy of the s o l i d product,

and the d i f f e r e n c e i n metal-halogen bond energy may be

s u f f i c i e n t to s h i f t the r e a c t i o n from s o l v o l y s i s to

solvation. It i s d i f f i c u l t to e x p l a i n however, i n the

vanadium p e n t a f l u o r i d e r e a c t i o n s w i t h ammonia and

ethylenediamine, why a filacer Ine atom i s removed and remains

as a r e a c t i v e s p e c i e s i n an amine w i t h r e p l a c e a b l e hydrogen

atoms a v a i l a b l e to form hydrogen f l u o r i d e .

It has a l s o been implied ..that the f l u o r i n e b r i d g e

bond, which i s thought to e x i s t i n $iq.uiduvanadium penta-

f l u o r i d e , i s preserved i n the f o r mat ion,..of "the polymeric

VF^.Base complexes and that a vanadium - f l u o r i n e bond t h a t

i s not involved i n b r i d g i n g i s broken. However t h e r e i s

no apparent reason why a b r i d g e bond, which would probably

be a weaker bond than a non-bridging bond, should be

preserved i n the r e a c t i o n . Muetterties has suggested that

'strong 1
f l u o r i n e b r i d g e bonds are formed i n s o l i d TeP4 (9)

to account f o r i t s extremely h i g h l a t t i c e energy. It i s

t h e r e f o r e p o s s i b l e that the bonds i n v o l v e d i n reactions

 - 52 -
o f vanadium p e n t a f l u o r i d e eould be 'strong' f l u o r i n e

bridge bonds,however i n view o f the l a c k o f information

about the s t r e n g t h and n a t u r e o f the f l u o r i n e b r i d g e

bond i t i s not p o s s i b l e to make any p r e d i c t i o n s about

its behaviour.

The l a c k o f s o l v o l y s i s o f the f l u o r i d e s expresses

a d i f f e r e n c e i n bond type and bond energy between

f l u o r i d e s and chlorides. Because o f the complex n a t u r e

of the f a c t o r s i n v o l v e d i n the energy requirements o f a

r e a c t i o n i t i s not p o s s i b l e to a t t r i b u t e the l a c k o f

s o l v o l y s i s to a d e f i n i t e cause. Further study o f the

r e a c t i o n s i s n e c e s s a r y to o b t a i n a more complete under-

standing of the f a c t o r s i n v o l v e d i n the f l u o r i n e bond

f o r m a t i o n and i t s i n f l u e n c e on the s t r u c t u r e and

p r o p e r t i e s o f the f l u o r i d e s .
 - 53 -

CHAPTER £ : THE NUCLEAR MAGNETIC RESONANCE SPECTRUM

OF VANADIUM PENTAFLUORIDE

In recent years s t r u c t u r a l s t u d i e s o f t h e simple

f l u o r i d e s have been g r e a t l y aided by the use o f n u c l e a r

magnetic resonance spectroscopy. I t has been p o s s i b l e

i n some cases to r e s o l v e the spectrum s u f f i c i e n t l y to

enable i n t e r p r e t a t i o n o f t h e resonance peaks i n terms

o f a d e f i n i t e s t r u c t u r a l model. Sulphur tetrafluoride

thus has been shown to have a t r i g o n a l bipyramid

s t r u c t u r e (with a lone p a i r occupying a t r i g o n a l planar

p o s i t i o n ) . o n the b a s i s o f i t s NMR spectrum (9). Structural

d e t e r m i n a t i o n s using other techniques have v e r i f i e d this

result.

It has not been p o s s i b l e to r e s o l v e the spectrum

o f a l l simple f l u o r i d e s although many attempts have been

made to do s o . M u e t t e r t i e s and P h i l l i p s ( 9 ) have i n -

v e s t i g a t e d many simple f l u o r i d e s and have obtained r e s o l v e d

s p e c t r a i n many c a s e s . They a l s o r e p o r t a number o f

chemical s h i f t v a l u e s f o r t h e f l u o r i d e s s t u d i e d . The

broad, unresolved F ^ resonance1

l i n e s obtained have been

attributed to t h e presence o f a r a p i d exchange process

i n v o l v i n g a s s o c i a t i o n through the f o r m a t i o n o f f l u o r i n e

b r i d g e bonds and perhaps, i n addition, a self-dissociation

into i o n i c species. These processes have been d i s c u s s e d

in earlier chapters.
 - 54 -
The n u c l e a r magnetic resonance study o f vanadium

p e n t a f l u o r i d e was undertaken w i t h a view to o b t a i n i n g

more i n f o r m a t i o n about i t s s t r u c t u r e and mode o f a s s o c i a t i o n .

The p r e l i m i n a r y r e s u l t s r e p o r t e d here have not yet r e a l i z e d

t h i s aim and f u r t h e r study i s n e c e s s a r y . The resonance

spectrum obtained w i t h vanadium p e n t a f l u o r i d e was a very

broad, unresolved peak from which o n l y the c h e m i c a l s h i f t

could be o b t a i n e d . T h i s broadening can be a t t r i b u t e d to

two s o u r c e s .

Vanadium has a n u c l e a r s p i n o f 7/2, and associated

w i t h i t an e l e c t r i c quadrupole moment. The presence o f

a quadrupole moment i s known to broaden a n u c l e a r

resonance s i g n a l and i n some cases the n u c l e a r quadrupole

broadening makes the resonance s i g n a l d i s a p p e a r completely.

The spectrum can sometimes be r e s o l v e d by c o o l i n g the

sample to a low temperature which reduces the r a t e o f

quadrupole r e l a x a t i o n o f the n u c l e a r resonance signal

s u f f i c i e n t to o b t a i n a spectrum i n which the o r i e n t a t i o n

o f the magnetic s t a t e s o f the n u c l e a r quadrupole i s

e f f e c t i v e l y constant. The F 1 0 /
resonance spectrum r e s o l v e d

by t h i s method would c o n s i s t o f (2J>1) l i n e s , where J i s

the n u c l e a r s p i n o f the c e n t r a l atom, f o r each set o f

equivalent F 1 0 /
nuclei. In the case where the c e n t r a l atom

i s vanadium w i t h J = 7/2, a t o t a l o f 8 l i n e s per set o f

equivalent F 1 0 /
n u c l e i would be o b t a i n e d .

It was mentioned e a r l i e r that vanadium p e n t a f l u o r i d e

i s probably a s s o c i a t e d through the f o r m a t i o n o f f l u o r i n e

 - 55 -

b r i d g e bonds and i n addition s e l f - i o n i s a t i o n i s also

thought to o c c u r . The e f f e c t of these processes i s the

t r a n s f e r of f l u o r i n e from one vanadium nucleus to

another r e s u l t i n g i n exchange broadening o f the n u c l e a r

resonance signal. The spectrum can be r e s o l v e d i n some

cases by d e c r e a s i n g the r a t e of exchange through cooling

of the sample.

In analogy w i t h the n u c l e a r resonance spectrum o f

antimony p e n t a f l u o r i d e ( 8 ) , vanadium p e n t a f l u o r i d e would

probably have at l e a s t t h r e e sets o f e q u i v a l e n t n u c l e i .

Each o f these s e t s could be s p l i t i n t o eight components

by the n u c l e a r s p i n o f vanadium. Thus i f the n u c l e a r

resonance spectrum o f vanadium p e n t a f l u o r i d e can be

r e s o l v e d i t w i l l probably be q u i t e c o m p l i c a t e d . Resolution

may be p o s s i b l e at low temperatures where both the

quadrupole and exchange broadening can be removed but i n

order to work at low temperatures, that i s about -100°C,

i t w i l l be n e c e s s a r y to f i n d a s o l v e n t f o r vanadium penta-

f l u o r i d e because i t s m e l t i n g point i s 1 9 . 5 ° C .

The chemical s h i f t i s d e f i n e d by the r e l a t i o n :

a Hs-Hr x 1 0 ^ (at constant frequency)

Hr

"where: % = the chemical s h i f t i n ppm

Hs s the resonant f i e l d s t r e n g t h f o r the sample
Hr = the resonant f i e l d s t r e n g t h f o r the r e f e r e n c e

The chemical s h i f t i s a f u n c t i o n o f the e l e c t i o n

d e n s i t y around the nucleus and thus w i l l be dependent on

 - 56 -

the type o f bond formed, the r e l a t i v e e l e c t r o n e g a t i v i t y

v a l u e s o f the atoms i n v o l v e d and o t h e r parameters. Because

the r e l a t i o n s h i p s are complex and not f u l l y understood,

the f a c t o r s i n f l u e n c i n g the chemical s h i f t w i l l not be

discussed here. The chemical s h i f t of vanadium penta-

f l u o r i d e has been found to be - 3 3 5 PPP r e l a t i v e to a

t r i f l u o r o a c e t i c acid reference. This value i s i n

agreement w i t h the chemical s h i f t s o f h e x a f l u o r i d e s o f

n e i g h b o r i n g elements. The chemical s h i f t v a l u e s o f

molybdenum and tungsten h e x a f l u o r i d e s are - 3 5 5 and

-242 ppm, r e s p e c t i v e l y , r e l a t i v e to t r i f l u o r o a c e t i c a c i d

(9). The v a l u e s f o r niobium and tantalum p e n t a f l u o r i d e s

are not known.

 - 57 -

CHAPTER 8; EXPERIMENTAL

(i) General Techniques:

Early investigators often reported that many fluorides,

in' particular volatile fluorides, attacked glass thus

prohibiting the use of glass apparatus i n studies of

fluorides. Recent workers (27) have shown that volatile

transition metal fluorides can be manipulated in glass

vacuum systems without etching provided that hydrogen

fluoride and traces of moisture are absent. Traces of

hydrogen fluoride, a common i m p u r i t y i n the preparation

of fluorides, can be removed by passing or collecting

the fluoride over carefully dried sodium fluoride,

where the hydrogen fluoride i s absorbed, forming stable

sodium bifluoride.

The marked suceptibility of volatile fluorides to

moisture i s due to the autocatalytic nature of the

hydrolysis reaction.

MF n + H 0 2
M 0 F
n _ 2
+ 2 H F

hRF + Si0 -^,SiFi 2 + * 2H 0 2

MF n + H 0 2 —»-etc.

Thus minute traces of moisture i n glass apparatus

can completely decompose the fluoride,.

Reactive volatile transition metal fluorides have been

found to a t t a c k vacuum grease, even the fluorinated greases.

Hence glass taps and ground joints which require vacuum

grease can not be used i n the apparatus.

 - 58 -

P u r i f i c a t i o n and general manipulation of a volatile

t r a n s i t i o n m e t a l f l u o r i d e , such as vanadium pentafluoride,

can be done i n s i m p l e all-glass distillation systems w h i c h

have been d e s c r i b e d by many e a r l i e r w o r k e r s . A typical

system c o n s i s t e d of three or f o u r traps connected via

capillary constrictions. E a c h t r a p was f i t t e d with a glass

break s e a l . A f t e r thoroughly flaming the system i n vacuo,

the capillary l e a d i n g to the vacuum m a n i f o l d was sealed

off l e a v i n g an all-glass, g r e a s e and moisture free distilla-

tion line. After distillation of v o l a t i l e m a t e r i a l s , the

interconnecting c a p i l l a r i e s were s e a l e d o f f and the contents

of the t r a p c o u l d be t r a n s f e r r e d , by connecting the trap

through i t s break s e a l , to another s i m i l a r system. This

technique, while making p o s s i b l e the study of the chemical

properties of the r e a c t i v e t r a n s i t i o n metal f l u o r i d e s ,

necessitates the continual, rather l a b o r i o u s , assembly of

such d i s t i l l a t i o n systems.

The suceptibillty of the f l u o r i d e s to hydrolysis

r e q u i r e s , i n a d d i t i o n to v i g o r o u s l y d r i e d apparatus, that

all the reagents placed i n contact with the f l u o r i d e be

p e r f e c t l y f r e e of t r a c e s of moisture. B e f o r e r e a c t i o n v/ith

the f l u o r i d e a l l the m a t e r i a l s used i n t h i s s t u d y were

distilled s e v e r a l times from d r y i n g agents i n all-glass,

g r e a s e and m o i s t u r e f r e e systems t h a t have j u s t been described.

The v o l a t i l e p r o d u c t s of the nitrogen base reactions

were i d e n t i f i e d p r i n c i p a l l y by the use of i n f r a r e d

 - 59 -

spectroscopy. A l l s p e c t r a were measured on a P e r k i n - E l m e r •

"model 2 1 " o r " I n f r a c o r d " r e c o r d i n g s p e c t r o p h o t o m e t e r s

equipped w i t h sodium chloride optics. Gaseous m a t e r i a l s

w e r e c o n t a i n e d i n a 1 0 cm. cell. The liquid materials

were g e n e r a l l y p r e p a r e d as t h i n f i l m s between sodium

chloride plates. S o l i d s were p r e p a r e d as m u l l s or

p o t a s s i u m bromi.de pellets.

X - r a y powder p h o t o g r a p h s o f the s o l i d p r o d u c t s were

t a k e n on a G e n e r a l E l e c t r i c s o u r c e w i t h Copper radiation

and n i c k e l f i l t e r s . The c a m e r a , s u p p l i e d by General

E l e c t r i c , was of a c o n v e n t i o n a l d e s i g n having a circumference

of U-5 cm. Some o f t h e X - r a y p h o t o g r a p h s were k i n d l y taken

by D r . R. H. Thompson o f t h e G e o l o g y Dept. of this

University. The samples were s e a l e d i n t h i n w a l l e d 0.5

mm diameter c a p i l l a r i e s to prevent h y d r o l y s i s of the

sample d u r i n g the photographing.

Magnetic suceptibilities of the s o l i d s were measured

o n a Gouy b a l a n c e . A V a r i a n #+00*+ magnet w i t h 2 inch

tapered pole f a c e s s u p p l i e d a magnetic field of

a p p r o x i m a t e l y 15,000 g a u s s . The magnetic moment was

c a l c u l a t e d f r o m t h e w e i g h t g a i n o f t h e unknown s o l i d on

a p p l i c a t i o n o f the magnetic field and the w e i g h t g a i n of

an e q u a l v o l u m e o f a r e f e r e n c e s o l i d , (mercuric

c o b a l t i t e t r a t h i o c y a n a t e , H g C o t S C N ) ^ ) o f known suceptibility,

i n t h e same t u b e and v / i t h t h e same f i e l d strength. A l l

s u c e p t i b i l i t i e s w e r e m e a s u r e d a t r.oom t e m p e r a t u r e .
 - 60 -

The d i s s o c i a t i o n pressure of an e a s i l y hydrolyzed

solid can be r e a d i l y determined w i t h an ail-glass spiral

gauge w h i c h h a s been d e s c r i b e d previously (27)

The apparatus consisted of a P y r e x s p i r a l attached

to a small sample-containing bulb. The spiral was encased

i n a g l a s s e n v e l o p e w i t h an o p t i c a l face opposite the point •

where a m i r r o r was attached to the spiral. Deflections

of the spiral c a u s e d by p r e s s u r e differences could be detected

with a suitable optical system. The spiral gauge was not

c a l i b r a t e d but r a t h e r was u s e d as a n u l l - p o i n t i n s t r u m e n t

i n conjunction with a m e r c u r y manometer.

The s a m p l e bult>- was connected v i a ,a side arm, t o the

vacuum m a n i f o l d so t h a t b o t h s i d e s o f the spiral gauge

c o u l d be evacuated. The s i d e arm was constricted close to

the sample b u l b t o f a c i l i t a t e sealing off. A B-10 socket

was joined to the s i d e arm, above the capillary constriction,

through w h i c h the s a m p l e c o u l d be introduced.

The solid sample was placed i n a bent tube i n a

d r y - b o x and connected to the d i s s o c i a t i o n p r e s s u r e apparatus

v i a . t h e B-10 joint. Sealing of the j o i n t was accomplished

with a Teflon s i e v e , t h e u p p e r edge of w h i c h was lightly

s m e a r e d w i t h vacuum g r e a s e . The s y s t e m was evacuated, the

P y r e x s p i r a l f l u s h e d w i t h d r y a i r s e v e r a l t i m e s and the

s m a l l bulb at the base of the s p i r a l was flamed.. When

t h e a p p a r a t u s was dry the b e n t t u b e was twisted through

l 8 0 ° and the sample poured t h r o u g h the capillary into the

 - 61 -

bulb. The c a p i l l a r y was s e a l e d o f f l e a v i n g t h e sample

i n an a l l g l a s s system. The d i s s o c i a t i o n pressure

of the s o l i d c o u l d t h e n be m e a s u r e d w i t h a minimum o f

hydrolysis.
 - 62 -

( i i ) ANALYTICAL METHODS;

The compositions of t h e s o l i d products obtained i n

the r e a c t i o n s o f n i t r o g e n b a s e s w i t h t h e p e n t a f l u o r i d . e s were

determined by q u a n t i t a t i v e a n a l y s i s of t h e elements present.

I n a l l c a s e s , s t a n d a r d methods were used. A l l microanalyses

for c a r b o n a n d h y d r o g e n w e r e done b y D r . A l f r e d Bernhardt,

M u l h e i m , Germany.

(a) Vanadium:

A dilute (1%) s u l p h u r i c a c i d s o l u t i o n o f t h e sample

was o x i d i z e d t o the pentavalent state w i t h excess permanga-

nate. The v a n a d i u m was t h e n r e d u c e d t o the t e t r a v a l e n t state

by b a b b l i n g s u l p h u r d i o x i d e i n t o t h e s o l u t i o n f o r 10 t o

Vy m i n u t e s . Excess s u l p h u r d i o x i d e was r e m o v e d by b o i l i n g

the s o l u t i o n . T e t r a v a l e n t v a n a d i u m was t h e n o x i d i z e d t o

p e n t a v a l e n t v a n a d i u m by t i t r a t i o n w i t h s t a n d a r d (O.OlN)

p o t a s s i u m permanganate u n t i l t h e permanganate c o l o r became

visible. I n compounds where l o w e r v a l e n c y s t a t e s o f v a n a d i u m

w e r e s u s p e c t e d , t h e sample was t i t r a t e d w i t h O.OlN p e r m a n g a -

nate immediately a f t e r d i s s o l v i n g i ndilute sulphuric acid

s o l u t i o n and t h e n t h e above p r o c e d u r e was r e p e a t e d . I n this

way the presence of t r i v a l e n t or t e t r a v a l e n t vanadium i n

the product c o u l d be d e t e c t e d .

(b) Niobium:

The s a m p l e was d i s s o l v e d i n w a t e r a n d t h e s o l u t i o n made

a l k a l i n e w i t h ammonium h y d r o x i d e . The r e s u l t a n t precipitate

o f h y d r a t e d n i o b i u m o x i d e was i g n i t e d t o n i o b i u m pentoxide

and weighed.
 - 63 -

I n t e r f e r e n c e by e t h y l e n e d i a m i n e i n the estimations of

n i o b i u m and v a n a d i u m was p r e v e n t e d by digestion of the sample

with concentrated sulphuric a c i d and mercuric oxide (as in

the Kjeldahl method f o r n i t r o g e n ) w h i c h d e s t r o y e d the

ethylene diamine. The s a m p l e was then d i l u t e d with water

and the m e t a l e s t i m a t e d as a b o v e . I n the vanadium

e s t i m a t i o n mercury, which p r e c i p i t a t e d d u r i n g the reduction

with sulphur dioxide, was filtered off before titration

with standard permanganate,

(c) Fluorine:

I t was f o u n d t o be quite difficult to obtain reproducible

fluorine analyses, especially i n the v a n a d i u m compounds.

Several different g r a v i m e t r i c methods were investigated;

namely p r e c i p i t a t i o n of f l u o r i n e as calcium floride,

triphenyltin fluoride or lead chlorofluoride. The most

c o n v e n i e n t and most r e l i a b l e g r a v i m e t r i c method was found

to be p r e c i p i t a t i o n as lead chlorofluoride. Trpheny^tin

f l u o r i d e p r e c i p i t a t i o n did not g i v e good r e s u l t s . Calcium

fluoride precipitation requires a coprecipitation step with

c a l c i u m c a r b o n a t e and offers no advantage over lead chloro-

fluoride. The s i m p l i c i t y of lead chlorofluoride precipita-

t i o n and the large conversion factor of l e a d chlorofluoride

make t h i s a more s u i t a b l e method t h a n c a l c i u m fluoride

precipitation.

V o l u m e t r i c d e t e r m i n a t i o n of f l u o r i d e w i t h thorium

nitrate solution i s s u p p o s e d t o be r e l i a b l e however the

 - 64 -

difficulty of observing the endpoint of the t i t r a t i o n requires

much p r a c t i c e w i t h t h e m e t h o d b e f o r e r e l i a b l e r e s u l t s can

be o b t a i n e d . T h i s method i s n o t s u i t a b l e f o r o c c a s i o n a l

fluorine analyses.

Regardless o f t h e method o f p r e c i p i t a t i o n u s e d , a

preliminary s e p a r a t i o n of f l u o r i n e from i n t e r f e r i n g ions i s

necessary. Distillation o f f l u o r i d e as fluorosilicic

a c i d from a constant b o i l i n g (135° ) C

mixture of s u l p h u r i c

acid quantitatively separates f l u o r i d e fromm a l l o t h e r

c a t i o n s and a n i o n s (33). The d i s t i l l a t e contains only silicon

and fluorine (presumably as S i F ^ ) and f l u o r i d e

=
c a n be

determined by a n y o f t h e m e t h o d s d i s c u s s e d p r e v i o u s l y .

T h i s s e p a r a t i o n has t h e w i d e s t a p p l i c a b i l i t y as w e l l as

being t h e most r e l i a b l e . P r e c i p i t a t i o n o f i n t e r f e r i n g

metal ions with specific a n a l y t i c a l p r e c i p i t a n t s was n o t

as s a t i s f a c t o r y as d i s t i l l a t i o n .

F l u o r i n e a n a l y s e s w e r e done a c c o r d i n g t o the f o l l o w i n g

method. A w e i g h e d s a m p l e was d r o p p e d i n t o 75 m l . o f 33%

sulphuric acid s o l u t i o n i n a 250 m l . d i s t i l l i n g f l a s k equipped

w i t h a thermometer, a dropping f u n n e l and a condenser. The

s o l u t i o n was b r o u g h t t o t h e b o i l and t h e b o i l i n g liquid was

maintained between 1 0 3 and 135°C by a d d i n g water s l o w l y from

the dropping funnel. The d i s t i l l a t i o n was c o n t i n u e d until

250 m l . o f d i s t i l l a t e was c o l l e c t e d . The d i s t i l l a t e was

neutralized with dilute sodium h y d r o x i d e , using bromphenol

b l u e i n d i c a t o r , a n d one m l . o f c o n c e n t r a t e d h y d r o c h l o r i c
 - 65 -

a c i d added. The d i s t i l l a t e was t h e n h e a t e d and 5 gm. o f

lead, n i t r a t e d i s s o l v e d i n t h e w a t e r when i t r e a c h e d 70°.

Five gm. o f s o d i u m . a c e t a t e w e r e added when t h e s o l u t i o n was

a b o u t 95°C. The s o l u t i o n was k e p t h o t f o r one hour and

allowed to cool overnight. The p r e c i p i t a t e o f l e a d

c h l o r o f l u o r i d e was f i l t e r e d i na glass c r u c i b l e , washed

with saturated lead chlorofluori.de s o l u t i o n , d r i e d a t lhO°C

and weighed,

(d) Nitrogen:

N i t r o g e n was d e t e r m i n e d i n p y r i d i n e and e t h y l e n e d i a m i n e

derivatives by d i g e s t i n g t h e sample w i t h cone, sulphuric

a c i d , p o t a s s i u m s u l p h a t e and m e r c u r i c o x i d e f o l l o w e d by

s t e a m d i s t i l l a t i o n o f ammonia f r o m c o n e , a l k a l i into

boric acid solution. The e v o l v e d ammonia w a s t i t r a t e d with

standard (0.01N)' h y d r o c h l o r i c
1
a c i d using methylene blue-

methyl red i n d i c a t o r . The d i g e s t i o n s t e p was o m i t t e d i n

the ammonia d e r i v a t i v e s ; t h e s a m p l e b e i n g a d d e d t o c o n e ,

a l k a l i and steam d i s t i l l e d as i n the s t a n d a r d procedure.

M i c r o a n a l y s e s o n some o f t h e s a m p l e s b y D r . B e r n h a r d t

p r o v i d e d a check on t h e method.
 • - 66 -

(iii) FLUORINE SUPPLY:

Fluorine was s u p p l i e d by the Allied Chemical Co. i n a

steel gas cylinder containing s i x pounds of fluorine at

400 p.s.i. The cylinder was installed i n an upright position

in a walk-in fume hood and shielded with a brick screen to

minimize the spreading of any violent reaction which might

occur upon entry of high pressure fluorine into the regulating

system. Reduction of the gas pressure was achieved with

two stainless steel needle valves (Hoke type 316 No. 134311)

in series. The high pressure gas line was constructed from

£ - inch stainless steel pressure tube, threaded and silver

soldered at a l l joints.

On the low pressure side of the needle valves

copper tubing, connected with brass compression fittings, was

used. In the low pressure line, directly after the reducing

needle v a l v e s was a blow-off consisting of silver soldered

T - j o i n t 'of ? " copper tubing with outlet dipping into a test-

tube of F l u o r o l u b e o i l (Hooker Chemical Co.,; FS-5). The

'blow-off, originally intended as a safety device to prevent

a dangerous buildup of pressure i n the copper line, eventually

served as a crude flow meter ?;hen t h e original flowmeter

failed to function. The flowwas roughly estimated by count-

ing the bubbles emerging through the blow-off when the top

at the exit of the low pressure line was closed.

Next to the blow-off was an 8" copper tube, |-" i n

diameter,containing sodium "fluoride pellets to remove traces

 - 67 -
of hydrogen f l u o r i d e . A d i f f e r e n t i a l manometer f l o w meter

f o l l o w e d the hydrogen f l u o r i d e absorber. The flow meter

c o n s i s t e d of a g l a s s U-tube f i l l e d w i t h F l u o r o l u b e o i l

( H o o k e r C h e m i c a l Co.; FS-5) and connected v i a T e f l o n

tubing to % n
copper tube sidearms j o i n e d w i t h a silver

s o l d e r e d T - j o i n t t o the gas.flow line. The sidearms had

e x p a n s i o n chambers ( l " d i a m e t e r and 2" l o n g ) w i t h sufficient

volume to c o n t a i n a l l the manometric f l u i d i n case i t

was d i s p l a c e d by sudden a p p l i c a t i o n of a h i g h pressure.

The pressure d i f f e r e n c e v/as c r e a t e d w i t h a T e f l o n d i a p h r a g m ,

punctured with a small hole, placed i n the flow line between

the two arms o f t h e manometer. A n i c k e l by-pass valve was

c o n n e c t e d i n p a r a l l e l w i t h the d i a p h r a g m so t h a t once the

f l o w r a t e had been determined the pressure c o u l d be equalized

and the flowmeter bypassed. This bypass v a l v e a l s o permitted

passage of f l u o r i n e i n the event of b l o c k a g e i n the flow-meter.

A brass needle valve (Hoke no. ^31) f o l l o w e d the flowmeter

permitting the fluorine supply t o be turned o f f at this point.

A brass T - j o i n t was n e x t i n the line to permit mixing

d r y n i t r o g e n w i t h the f l u o r i n e . A brass needle valve (Hoke

no. *+3l) was i n c l u d e d i n the nitrogen inlet. The mixed

gases t h e n were passed from the T - j o i n t through a brass needle

valve (Hoke n o . k$l) into the r e a c t i o n systems w h i c h were

connected to the f l u o r i n e r e g u l a t i n g system at t h i s point

with brass compression fittings.

 - 68 -

(iv) PREPARATION OF VANADIUM AND NIOBIOM PENTAFLUORIDES

Vanadium and n i o b i u m p e n t a f l u o r i d e s were p r e p a r e d by

f l u o r i n a t l o n o f t h e powdered m e t a l s a t 300 - 325°C a s

described p r e v i o u s l y (1*0. F l u o r i n a t i o n s w e r e done ina

n i c k e l r e a c t o r tube 12 i n s . l o n g and 1 i n . d i a m e t e r with

one e n d o p e n a n d f l a n g e d to permit the e n t r y of n i c k e l boats

containing t h e powdered m e t a l . The l a r g e opening'was

s e a l e d by b o l t i n g a n i c k e l p l a t e , w i t h a exit tube

silver soldered t o i t , t o the flange,-compressing a lead

w a s h e r t o make a g a s t i g h t seal. The exit tube i n t h e

f a c e p l a t e was c o n n e c t e d t o t h e c o l l e c t i o n system w i t h a brass

compression f i t t i n g . The o t h e r e n d o f t h e n i c k e l t u b e was

silver soldered t o a l e n g t h of % i n . n i c k e l tubing which

c o u l d be c o n n e c t e d t o t h e f l u o r i n e supply line with a

i i n . compression fitting.

The f l u o r i d e s w e r e c o l l e c t e d i n g l a s s t r a p l i n e s , t h e

design of w h i c h depended on t h e f l u o r i d e being prepared.

V a n a d i u m p e n t a f l u o r i d e was c o l l e c t e d i n a s i m p l e distillation

line of four t r a p s , t h e two f o l l o w i n g t h e r e a c t o r being

equipped w i t h capillary c o n s t r i c t i o n s i n e a c h arm a n d a

breakseal. The r e m a i n i n g two t r a p s s e r v e d t o p r e v e n t back

d i f f u s i o n of moisture i n t o the t r a p s c o l l e c t i n g v a n a d i u m pent-

af l u o r i d e . Niobium p e n t a f l u o r i d e , being less volatile was

collected i n a similar t r a p l i n e but with the breakseals omitted

as t h e f l u o r i d e was t r a n s f e r r e d t o s m a l l b u l b s i na

d r y box i m m e d i a t e l y b e f o r e performing a reaction, instead

 - 69 -
of by distillation.

To p r e p a r e t h e f l u o r i d e , a b o u t t e n grains o f t h e p o w d e r e d

m e t a l was p l a c e d i n a n i c k e l b o a t (6 i n . l o n g , 3/*+ i n . w i d e )

w h i c h was t h e n p l a c e d i n the n i c k e l reactor tube. The

f l a n g e was b o l t e d i n t o p l a c e and t h e n t h e n i c k e l tube

was placed i n a tube f u r n a c e and connected t o the f l u o r i n e /

nitrogen supply l i n e , with a brass compression fitting.

The r e a c t o r was h e a t e d t o 300°C a n d n i t r o g e n p a s s e d f o r

two h o u r s t o remove a l l t r a c e s o f m o i s t u r e f r o m t h e m e t a l

and r e a c t o r . A glass trapline was t h e n c o n n e c t e d t o t h e

e x i t o f t h e n i c k e l r e a c t o r w i t h a c o m p r e s s i o n f i t t i n g and

d r y n i t r o g e n was p a s s e d f o r s e v e r a l h o u r s (generally

overnight). The g l a s s t r a p l i n e was p e r i o d i c a l l y flamed

w i t h a hand t o r c h a n d t h e n i c k e l t u b e was m a i n t a i n e d a t

200 - 300°C d u r i n g the passage of n i t r o g e n t o ensure the

complete removal o f moisture. The g l a s s t r a p s w e r e t h e n

chilled with d r y i c e - a l c o h o l baths, the metal heated

t o 325 - 350°C a n d f l u o r i n e gas, d i l u t e d w i t h dry nitrogen,

passed i n t o thereactor and t h e p r o d u c t s were collected

in the f i r s t two t r a p s . The b e s t y i e l d s o f t h e p e n t a f l u o r i d e

were o b t a i n e d when t h e f l u o r i n e concentration was s u f f i c i e n t l y

high t o ignite the metal. On c o m p l e t i o n o f t h e f l u o r i n a t i o n ,

d r y n i t r o g e n was p a s s e d f o r one h o u r t o remove u n r e a c t e d

f l u o r i n e from the system and t h e g l a s s traps sealed o f f

u n d e r vacuum.

Niobium p e n t a f l u o r i d e obtained i n t h i s manner was

 - 70 -
analyzed without f u r t h e r p u r i f i c a t i o n . Found: Nb., 49.3.

C a l c . f o r NbFtj: Nb, 49.4$. I t was stored i n sealed traps

u n t i l required and then t r a n s f e r r e d t o r e a c t i o n tubes i n

a d r y box. The lower r a t e o f h y d r o l y s i s and t h e much lower

v o l a t i l i t y o f niobium p e n t a f l u o r i d e r e l a t i v e to vanadium

p e n t a f l u o r i d e made t h i s procedure p o s s i b l e .

Vanadium p e n t a f l u o r i d e prepared i n t h i s manner was

distilled under vacuum onto c a r e f u l l y d r i e d sodium

f l u o r i d e and then i n t o g l a s s t r a p s equipped w i t h breakseals.

I t was found to be a white s o l i d melting about 20°C to a

pale straw coloured liquid as p r e v i o u s l y reported (4). A

sample o f the product was analysed according to t h e methods

previously described.

Found: V, 35.3; F, 64.1$.

C a l c . f o r VF5: V, 34.9; F, 65.1$.
 - 71 -

(v) THE REACTION OF VANADIUM PENTAFLUORIDE WITH AMMONIA

Gaseous ammonia (Matheson Co.) v/as c a r e f u l l y d r i e d

by condensing i t onto m e t a l l i c sodium i n a c a r e f u l l y dried,

all-glass d i s t i l l a t i o n system. An e x c e s s v/as t h e n d i s t i l l e d

from sodium onto vanadium p e n t a f l u o r i d e and a l l o w e d to m e l t .

A r e d d i s h brown s o l i d a l o n g w i t h t r a c e s o f orange and y e l l o w

s o l i d s was formed on c o n t a c t o f gaseous ammonia w i t h

vanadium p e n t a f l u o r i d e . I n l i q u i d ammonia a r e d d i s h - b r o w n

s o l i d was formed which d i d n o t appear t o be s o l u b l e i n

an e x c e s s o f l i q u i d ammonia. The ammonia was k e p t l i q u i d

a t a p p r o x i m a t e l y -50°C f o r s e v e r a l hours t o a l l o w r e a c t i o n

t o t a k e p l a c e and t h e n the v o l a t i l e p r o d u c t s were f r a c t i o n a t e d

t h r o u g h a s e r i e s of t r a p s c o o l e d to 0°C, -78°C and -19.6°C

i n i c e , a l c o h o l -CO2 and l i q u i d n i t r o g e n b a t h s r e s p e c t i v e l y .

V o l a t i l e f r a c t i o n s , condensing a t - 1 9 6 ° and -78°C were

identified s p e c t r o s c o p i c a l l y as ammonia. No m a t e r i a l was

found t o condense a t 0°C.

The s o l i d r e m a i n i n g a f t e r removal o f the v o l a t i l e

m a t e r i a l s was a d r y , powdery, r e d d i s h - b r o w n s o l i d ' w h i c h lost

ammonia r e a d i l y , b u i l d i n g up a p r e s s u r e of NH3 when s e a l e d

i n tubes. T h i s r e d d i s h - b r o w n s o l i d was "pumped" f o r 20

hours w h i l e a t room t e m p e r a t u r e and the v o l a t i l e p r o d u c t s

condensed i n a l i q u i d nitrogen trap. The o n l y v o l a t i l e

p r o d u c t o b t a i n e d was ammonia. The r e d d i s h s o l i d , when

s u b j e c t e d t o t h i s t r e a t m e n t , became a b u f f - c o l o u r e d solid

w h i c h d i d n o t l o s e ammonia on s t a n d i n g . An X - r a y powder
 - 72 -
photograph of the latter solid Indicated the presence of

ammonium fluoride i n the product.

The huff solid, which could be e x p o s e d t o the

atmosphere f o r short periods without appreciable hydrolysis,

was p l a c e d i n a bulb, heated to 100°C w i t h a n o i l b a t h

and " p u m p e d " f o r 120 hours. The v o l a t i l e products were

again condensed i n a liquid nitrogen trap. The original

buff solid decreased i n weight approximately 20$ and

slowly became darker i n colour. A white crystalline solid

which collected i n the outlet of the bulb and the liquid

nitrogen trap, was identified a s ammonium fluoride.

An X-ray photograph of the remaining brown solid

showed only faint lines i n the positions corresponding to

ammonium fluoride. Quantitative analysis of the product

indicated a composition VFL^NH^) with a small amount o f

ammonium fluoride remaining.

Found: V, 3^.7; F, 4$.8; NEU, 12.5$

C a l c . VF^CNH^): V , 35.4; F , 52.8; mi, 11.8$
C a l c . VFi+CNITC) <-) J

0.08 moleT ) V, 34.7; F, 53.1; NHo, 12.2$

NH^F ) J

The magnetic suceptibility of the s o l i d showed that

It was p a r a m a g n e t i c and the magnetic moment, on the basis

of t h e above composition, was calculated a s 2.1 Bohr magnetons.

The presence o f lower valency states of vanadium was confirmed

by dissolving t h e compound i n dilute sulphuric acid (1$)

and titrating directly with potassium permanganate. The

titre corresponded t o 44$ vanadium, indicating that about

8$ o f t h e v a n a d i u m was p r e s e n t i n the t e r v a l e n t state. I t

 - 73 -

was not p o s s i b l e t o account f o r t h i s i n the overall

composition of the product.

The infrared spectrum of t h e s o l i d , i n a KBr pellet,

showed t h e f o l l o w i n g a b s o r p t i o n s ( i n cm" ):1

3250 & 3i00
( s t r o n g and b r o a d b u t r e s o l v e d ) ; s h o u l d e r a t 2850;
1650 (weak and b r o a d ) ; l*+25 (strong); 980 (strong). A

p o s s i b l e weak a b s o r p t i o n o c c u r r e d a t 1075 b u t was not

resolved.

The s o l u b i l i t y of amminotetrafluorovanadium IV,

( N H ^ V F ^ , was investigated i n various solvents. The

s o l v e n t s used were d r i e d v/ith c r u s h e d p o t a s s i u m hydroxide

( e x c e p t e t h a n o l ) b e f o r e t h e compound was added. I t was

f o u n d t o be i n s o l u b l e i n b e n z e n e , carbon tetrachloride,

ethanol (100%), e t h e r , n i t r o b e n z e n e and p y r i d i n e . It

d i s s o l v e d i n water g i v i n g green coloured s o l u t i o n which

t u r n e d b l u e when a c i d i f i e d . The product appeared to

be i n h o m o g e n e o u s b e c a u s e t h e m a j o r p o r t i o n o f a sample

d i s s o l v e d immediately i n water l e a v i n g t r a c e s of a black,

difficultly s o l u b l e m a t e r i a l w h i c h e v e n t u a l l y went

into solution.

When a m m i n o t e t r a f l u o r o v a n o d i u m I V was heated i n

a d r y , sealed tube d e c o m p o s i t i o n o c c u r r e d about 250°0

accompanied by s e v e r e a t t a c k o f t h e g l a s s . A lustrous

b l a c k p o w d e r y m a t e r i a l was formed w h i c h was not identified.

 - 7k -
(vi) THE REACTION OF NIOBIUM PENTAFLUORIDE WITH AMMONIA

Ammonia was c a r e f u l l y d r i e d w i t h sodium metal

a s b e f o r e a n d a n e x c e s s was d i s t i l l e d onto niobium

pentafluoride. A r e a c t i o n o c c u r r e d i m m e d i a t e l y on m e l t i n g

t h e ammonia t o f o r m a y e l l o w s o l i d , a p p a r e n t l y i n s o l u b l e

i n e x c e s s l i q u i d ammonia. The v o l a t i l e c o n t e n t s were

distilled t h r o u g h two t r a p s c o o l e d t o -78° a n d -196 C. 0

The s o l i d m a t e r i a l was "pumped" h t o 5 h o u r s t h r o u g h these

same t r a p s . The f i n a l p r o d u c t o b t a i n e d v/as i d e n t i f i e d a s

diamminopentafluoroniobium V, ( N H ) N b F ^ , by a n a l y s i s .
3 2

Found: Nb, 4 l . 9 ; F, 1+1.5; NHo, 15.3$

C a l c . (NH ) NbJy
3 2 Nb, 41.9; F , 42.8; NH , 15.3$ 3

The p r o d u c t d i s s o l v e d q u i c k l y i n w a t e r a n d was h y d r o l y z e d

slowly i n moist a i r . Magnetic suceptibility measurements

showed t h e s o l i d was d i a m a g n e t i c , I n d i c a t i n g pentavalent

niobium. A n X - r a y powder p h o t o g r a p h d i d n o t show a n y l i n e s

t h a t c o u l d b e a t t r i b u t e d t o ammonium fluoride.

The i n f r a r e d spectrum o f (NH ) NbF^, p r e p a r e d a s a

3 2

KBr pellet, showed t h e f o l l o w i n g a b s o r p t i o n s ( i n c m " ) s 1

a b r o a d , s t r o n g b a n d w i t h a maximum a t 3250 and a shoulder

at 2850; 1650 ( v e r y , weak, b r o a d ) ; 1420 (strong); 1055

( v e r y w e a k ) ; 937 and 913 (strong, p a r t i a l l y resolved

d o u b l e t ) ; 800 (weak, b r o a d )

When h e a t e d i n a d r y , s e a l e d tube, '(NH ) NbF^ m e l t e d

3 2

about 300 - 310°C This melting point i s net r e l i a b l e

because c o n s i d e r a b l e a t t a c k o f the g l a s s tube o c c u r r e d upon

m e l t i n g which obscured the appearance of t h e sample. M e l t i n g was

 - 75 *
p r e s u m a b l y a c c o m p a n i e d by some decomposition.

The d i s s o c i a t i o n pressure o f ( N H 3 ) N b F ^ was m e a s u r e d

2

i n the a l l - g l a s s s p i r a l B o u r d o n gauge a p p a r a t u s described

earlier. The f o l l o w i n g results were obtained.

T (°K) ; I x 1 0 3 P(mm) log 1 Q P

318.1 3.144 1.5 0.176

232.2 3.09^ 2.0 0.301
327.7 3.051 2.5 0.398
332.8 3.005 2.9 0.462
337.7 2.966 3.3 0.519
342.6 2.919 3.9 0.591
348.0 2.874 4.9 0.690
352.3 2.840 5.5 0.740
357.7 2.795 6.4 0.806
362.7 2.757 7.5 0.875
367.2 2.723 8.9 0.949
373.2 2.677 10.7 1.029
From t h e s e values the p l o t o f l o g p v s . 1/T i s linear,

and obeys the. r e l a t i o n :

l o g P ( m m ) = 5.62
1 0 - 172.Q

Also using the r e l a t i o n :

Pi 2.303R k l
2 l
l }

AH = 7870 c a l / m o l e .
 - 76 -
(vii) THE REACTION OF VANADIUM PENTAFLUORIDE WITH PYRIDINE

Reagent grade p y r i d i n e (Eastman Kodak) was d r i e d by

distilling from crushed potassium hydroxide i n a d r y ,

a l l - g l a s s system. An excess o f d r y p y r i d i n e was distilled

onto vanadium p e n t a f l u o r i d e . Immediate r e a c t i o n occurred

forming a dark brown s o l i d which was i n s o l u b l e i n excess

pyridine. The v o l a t i l e m a t e r i a l s present were d i s t i l l e d

from the r e a c t i o n t r a p and separated i n t o a r b i t r a r y f r a c -

t i o n s condension at - 1 9 6 ° , - 78° and -23°C by c o o l i n g

a series of traps with l i q u i d nitrogen, d r y - i c e and

a l c o h o l and carbon t e t r a c h l o r i d e s l u s h baths r e s p e c t i v e l y .

The dark brown s o l i d remaining i n the t r a p was

not appreciably h y g r o s c o p i c and could be handled i n

a i r without n o t i c e a b l e decomposition. I t was identified

as p y r i d i n e t e t r a f l u o r o v a n a d i u m IV, (PyOVF^, by quantitative

analysis.

Found: V,24.6; F,35.0; N,6.2; C,30.3; H,3.5%

C a l c . f o r (Py)VF :V,24.7*,4 F,36.9; N,6.8; 0,29.2; H,2.4%

Magnetic s u c e p t i b i l i t y measurements i n d i c a t e d a

paramagnetic s o l i d and the magnetic moment c a l c u l a t e d f o r

(Py)VF 4 was i . 6 7 Bohr magnetons, c l o s e to the expected

v a l u e o f 1.73 f o r t e t r a v a l e n t vanadium. T i t r a t i o n with

standard (O.OlN) potassium permanganate immediately a f t e r

d i s s o l v i n g the sample i n d i l u t e s u l p h u r i c a c i d indicated

that a l l the vanadium was present i n the t e t r a v a l e n t

state.
 1

-77 -
No v o l a t i l e m a t e r i a l s w e r e f o u n d i n t h e -196°C fraction.

The l i q u i d found i n b o t h -7&° a n d -23°C f r a c t i o n s was identi-

fied s p e c t r o s c o p i c a l l y as p y r i d i n e . No i n f r a r e d e v i d e n c e

was f o u n d f o r f l u o r i n a t e d p y r i d i n e s , A reactive fluoride,

which bleached a zirconium n i t r a t e - a l i z a r i n t e s t paper,

was f o u n d i n t h e - 2 3 ° c
f r a c t i o n o f p y r i d i n e and s l i g h t

etching o f t h e g l a s s t r a p was o b s e r v e d when t h e t r a p

c o n t e n t s were d i s t i l l e d under non-anhydrous conditions.

I t was n o t p o s s i b l e t o i d e n t i f y t h e r e a c t i v e f l u o r i d e

present. No t r a c e o f f l u o r i d e was f o u n d i n t h e -78°C

pyridine fraction.

I n a second r e a c t i o n vanadium p e n t a f l u o r i d e was

s u b l i m e d onto the w a l l s of a l a r g e d i a m e t e r tube and

frozen with dry-Ice. P y r i d i n e v a p o u r , was p a s s e d o v e r t h e

s o i i d V F ^ w i t h t h e same r e s u l t a s b e f o r e . A d a r k brown

s o l i d was f o r m e d on immediate contact of p y r i d i n e with

v a n a d i u m p e n t a f l u o r i d e . w h i c h was i d e n t i f i e d a s ( P y ^ F ^ .

(found V, 2h.k%)

When h e a t e d i n a s e a l e d tube, p y r i d i n e t e t r a f l u o r o -

vanadium I V d i d n o t melt b u t r a t h e r decomposed about 150°C

y i e l d i n g a brown l i q u i d and a g r e e n i s h coloured solid.

The i n f r a r e d spectrum o f pyridinetetrafluorovanadium

I V showed many p e a k s I d e n t i c a l t o those found i n the

p y r i d i n e spectrum: The f o l l o w i n g a b s o r p t i o n peaks

( i n c m ) were o b s e r v e d :
- 1
3 1 0 0 ( v s ) , 2 8 0 0 ( s ) , 2150(w),

I850(w), 1685(shoulder), l 6 2 5 ( s ) , l5*K)(m), l V ? 5 ( s ) ,

 - 78 -
1325(w), 12o0(m), 12k5(m), 1200(m), 1175(m), 1 1 0 0 ( s h o u l d e r ) ,

1 0 6 0 ( s h o u l d e r ) , 1 0 5 0 ( s h o u l d e r ) , 980(broad), 855(vw),

7 8 0 ( s ) , 755(s).
 - 79 -

(viii) THE REACTION OF VANADIUM PENTAFLUORIDE WITH

ETHYLENEDIAMINE.

Reagent grade e t h y l e n e d i a m i n e (Eastman-Kodak) was

c a r e f u l l y d r i e d with crushed potassium hydroxide and

distilled, i n a n a l l - g l a s s vacuum system, onto vanadium

pentafluoride. A r e a c t i o n occurred immediately on

melting the e t h y l e n e d i a m i n e and a brown s o l i d , I n s o l u b l e

i n excess ethylenediamine was formed. Volatile materials

were d i s t i l l e d from the r e a c t i o n t r a p through a series

of t r a p s a r b i t r a r i l y c o o l e d t o - 1 9 6 ° C , - 7 8 ° C and -23 C
G

with liquid nitrogen, alcohol - C 0 2 and a carbon tetrachloride

slush respectively.

The v o l a t i l e m a t e r i a l s were r e a d i l y removed leaving

a d a r k brown p o w d e r y s o l i d f o u n d t o have t h e composition

VF (en)
! + 3

Found: V,l6.9; F , 2 k . 9 N , 2 k . l ; ; C,23.7; H,7.3#.

Calc. for VFi (en) :V,l6,7; F , 2 k . 8 ; N,27.1;
f 3 C,23.4; H,7.9%.

Magnetic s u e e p t i b i l i t y measurements i n d i c a t e d a

paramagnetic s o l i d and the magnetic moment, calculated

for t h e c o m p o s i t i o n V F i ( e n ) , was
+ 3 2 . 0 Bohr magnetons.

I t was not p o s s i b l e t o c o n f i r m the t e t r a v a l e n c y of

vanadium i n d i c a t e d by t h e m a g n e t i c measurements w i t h a

direct t i t r a t i o n because of the interference of

e t h y l e n e d i a m i n e w i t h the permanganate t i t r a t i o n . It

was f o u n d n e c e s s a r y t o remove e t h y l e n e d i a m i n e w i t h s t r o n g

oxidizing c o n d i t i o n s b e f o r e r e l i a b l e vanadium e s t i m a t i o n s

c o u l d be o b t a i n e d and so t h e l o w e r v a l e n c e s t a t e o f vanadium
 - 80 -

could not be preserved while removing ethylenediamine.

The v o l a t i l e m a t e r i a l s c o l l e c t e d i n -23°C and «78°C

t r a p s were i d e n t i f i e d s p e c t r o s c o p i c a l l y as ethylenediamine.

No t r a c e o f a r e a c t i v e f l u o r i d e was found i n the l i q u i d

fractions. The i n f r a r e d s p e c t r a o f the l i q u i d fractions

i n d i c a t e d that no f l u o r i n a t e d ethylenediamine was present.

No r e a c t i o n product was found i n the -196°C t r a p .

The i n f r a r e d spectrum of t r i s ( e t h y l e n e d i a m i n e ) t e t r a -

fluorovanadium IV, | v ( e n ) ^ | p , was 4 complex, resembling

the spectrum o f pure ethylenediamine. The following

a b s o r p t i o n peaks ( i n cm ), w i t h i n d i c a t e d r e l a t i v e intensity

were observed. 3 2 0 0 ( s ) , 3 H 0 ( s ) , 2490(s), 2340(shoulder),

2140(w), 1595(a), 1463(m), 1330(m), 1285(m), 1130(s),

1 0 5 0 ( s ) , 9 6 5 ( s ) , 725(broad). There were no a b s o r p t i o n

peaks that could be assigned to C-F v i b r a t i o n f r e q u e n c i e s

i n d i c a t i n g that the ethylenediamine i n the s o l i d was not

fluorinated i n the r e a c t i o n .

When heated i n a sealed tube the compound d i d not

melt but decomposed above l 6 0 ° C y i e l d i n g a mixture o f l i q u i d

and s o l i d products which were not i d e n t i f i e d . The

o r i g i n a l r e a c t i o n product, t r i s ( e t h y l e n e d i a m i n e ) t e t r a -

fluorovanadium IV was found to be i n s o l u b l e i n benzene,

e t h e r , e t h a n o l (100$), carbon t e t r a c h l o r i d e , nitrobenzene

and p y r i d i n e . I t d i s s o l v e d q u i c k l y i n water when s l i g h t l y

a c i d i f i e d with s u l p h u r i c a c i d . I t was not markedly

h y g r o s c o p i c and could be handled i n a i r without n o t i c e a b l e

decomposition.
 - 81 -

(ix) THE REACTION OF NIOBIUM PENTAFLUORIDE AND

ETHYLENEDIAMINE:

Reagent grade ethylenediamine (Eastman-Kodak) was

carefully d r i e d over crushed potassium hydroxide and d i s t i l l e d

i n vacuum i n an a l l - g l a s s apparatus. An excess was then

condensed, i n vacuum, onto niobium p e n t a f l u o r i d e ( 0 . 5 0 3

gm, 2 . 6 m i l l i m o l e s ) and melted. R e a c t i o n occurred s l o w l y

and the ethylenediamine s l o w l y turned y e l l o w . On standing

at room temperature f o r s e v e r a l hours, a dark brown

v i s c o u s syrup formed from which ethylenediamine could

o n l y be removed w i t h d i f f i c u l t y . The syrupy brown

contents o f the r e a c t i o n t r a p were heated to 90 - 95°C

and "pumped" f o r a t o t a l o f 12 hours which removed a l l

but 0.257 gm ( 4 . 3 m i l l i m o l e s ) o f ethylenediamine. During

removal o f ethylenediamine, the dark brown syrup was

seen to s l o w l y s o l i d i f y and become a g l a s s y , l i g h t brown

m a t e r i a l which could be e a s i l y crushed. The g a i n i n weight

of 0.257 gm corresponds to the formation o f a product

w i t h the o v e r a l l composition N b F ^ ( e n ) 1 . 6 . This

composition was confirmed by a n a l y s i s .

Found: Nb, 3 2 . 6 ; F, 33.4%
Calc. for NbF^(en) : Nb, 3 2 . 7 ;
1 # 6 F, 33.4%

The o n l y v o l a t i l e m a t e r i a l removed from the brown

syrup was ethylenediamine which was i d e n t i f i e d spectroscopi-

cally.

The s o l i d product, N b F ^ ( e n ) 5 , 1> was r e a d i l y soluble

i n water. I t was not a p p r e c i a b l y hygroscopic and could

 - 82 -

be h a n d l e d In a i r without noticeable decomposition. On

heating i n a s e a l e d tube d e c o m p o s i t i o n o c c u r r e d about

2kO°C y i e l d i n g a m i x t u r e o f u n i d e n t i f i e d s o l i d s and liquids.

Owing t o t h e i n d e f i n i t e n a t u r e o f t h e p r o d u c t , no further

i n f o r m a t i o n c o u l d be obtained.
 - 83 -
( x ) THE NUCLEAR MAGNETIC RESONANCE SPECTRUM OF VANADIUM
• PENTAFLUORIDE;

V a n a d i u m p e n t a f l u o r i d e was distilled twice i n vacuum

f r o m c a r e f u l l y d r i e d s o d i u m f l u o r i d e and t h e n c e i n t o a

h m.m. p y r e x t u b e w h i c h was then sealed off. The tube

containing vanadium p e n t a f l u o r i d e was then placed

i n s i d e a 5 mm pyrex tube. A few d r o p s of r e a g e n t

t r i f l u o r o a c e t i c : : a c i d was placed i n t h e 5 Rim t u b e and

frozen and t h e e x t e r n a l , 5 mm t u b e was then sealed o f f

under vacuum.

The f l u o r i n e resonance spectrum of vanadium

pentafluoride was m e a s u r e d a t room t e m p e r a t u r e w i t h a

Varian m o d e l ^OO-B high-resolution nuclear magnetic

resonance spectrometer equipped with a twelve inch

e l e c t r o m a g n e t , and a hO m e g a c y c l e radio frequency

oscillator. A megnetlc f i e l d s t r e n g t h of a p p r o x i m a t e l y

9000 g a u s s was used. The sample t u b e was spun f o r

increased resolution.

The chemical s h i f t of vanadium pentafluoride was

c a l c u l a t e d f r o m the l i n e a r d i s p l a c e m e n t of the F 1 0 ,

s i g n a l i n VF^ r e l a t i v e t o the F 1 D /
s i g n a l of the

t r i f l u o r o a c e t l c acid external reference. On the

assumption that the f i e l d sweep was l i n e a r , the c h e m i c a l

s h i f t m e a s u r e d was - 335 ppm.

' Only a broad r e s o n a n c e peak h a v i n g a w i d t h a t

h a l f - h e i g h t o f a p p r o x i m a t e l y 75 c p s was obtained for

vanadium pentafluoride. No a t t e m p t s t o r e s o l v e the

 - 84 -
s p e c t r u m , by l o w e r i n g t h e s a m p l e t e m p e r a t u r e , were

made b e c a u s e p u r e v a n a d i u m p e n t a f l u o r i d e f r e e z e s a t

19.5°C. A low m e l t i n g , n o n - r e a c t i n g s o l v e n t f o r vanadium

p e n t a f l u o r i d e has not y e t been f o u n d .

 • • > - 85 -

'•' REFERENCES

1. R u f f , 0., and L i c k f e t t , H.: B e r . (1911),. 4 4 , 2539.

2. F a i r b r o t h e r , F., and F r i t h , W.C.: J . Chem. Soc. (1951)» 3051.

3 . J u n k i n s , J . H., F a r r a r , R. L., B a r b e r , E. J . , and B e r n h a r d t ,
H. A.: J . Amer. Chem. S o c . ( 1 9 5 2 ) , £ 4 , 3^64.

4. C l a r k , H. C., and .Emeleus, II. J . : . J . Chem. Soc. ( 1 9 5 7 ) , 2119.

5. T r e v o r r o w , L. E., F i s c h e r , J . , and S t e u n e n b e r g , R. K.:
J . Amer. Chem Soc. ( 1 9 5 7 ) , 22., 5 l 6 5 .
6. C l a r k , H. C.: Chem. Revs. ( 1 9 5 8 ) , 58,.869.

7. Hoard, J . L.: J . Amer. Chem. Soc. ( 1 9 3 9 ) , 81? 1252.

8. Hoffman, C. J . . H o l d e r , B. E. , and J o l l y , W. j'.: J . Phys.
Chem. ( 1 9 5 8 ) , 62, 36*+.

9 . M u e t t e r t i e s , E. L., and P h i l l i p s , W. D.s J . Amer. Chem.

Soc. ( 1 9 5 9 ) , 8 1 , 1004.
10. Banks, A. A., Emeleus, H. J . , and Woolf, A. A.: J .
Chem. Soc. ( 1 9 4 9 ) , . 2 8 6 1 .
11. S h a r p , A. G., and Emeleus H. J . J J . Chem. Soc. ( 1 9 W , 2135.

1 2 . Emeleus, H. J . , and W o o l f , A. A.: J . Chem. Soc. (194-9), 2865.

13. F a i r b r o t h e r , F., F r i t h , W. C , and Woolf, A. A.: J .
Chem. Soc. ( 1 9 5 4 ) , 1031.

14. Emeleus, H. J . , and Gutmann, V., J . Chem. Soc. (19^9), 2979.

1 5 . C l a r k , H. C., and Emeleus, H. J . : J . Chem. Soc. ( 1 9 5 8 ) ,

190.

1 6 . C l a r k , H. C., and Emeleus, H. J . : J . Chem. S o c . ( 1 9 5 7 ) ,

4778.

17. G i l l e s p i e , R. J . , and Nyholm, R. S.: Q u a r t . Revs. (1957),

339.
1 8 . M u e t t e r t i e s , E i L . : J . Amer. Chem. S o c . ( i 9 6 0 ) , 8 2 , 1082.

19. F o w l e s , G. W. A., and P l e a s s , C. M.: Chem. and I n d . (1955)

1743.

2 0 . F o w l e s , G. W. A., and P l e a s s , C. M.: J . Chem. S o c . ( 1 9 5 7 ) ,

1674.
 - 86 -

21. F o w l e s , G. W. A., and P l e a s s , C. M.s J . Chem. S o c .

(1957), 2078.
22. F o w l e s , G. W. A. ? and P o l l a r d , F. H.: J . Chem. S o c .
(1952), 4938.
23. F o w l e s , G. W. A., and M c G r e g o r , W. R.s J . Chem. Soc
(1958), 136.
24. F o w l e s , G. W. A., and N i c h o l l s , D.: J . Chem. S o c .
(1958), 1687.
25. F o w l e s , G. W. A., a n d O s b o r n e , B. P.: J . Chem. S o c .
2275.
26. N y h o l m , R. S., C o m p l e x Compounds o f t h e T r a n s i t i o n M e t a l s ,
a R e p o r t t o t h e X S o l v a y C o u n c i l , B r u s s e l s , (1956).

27. C l a r k , H. C.s Ph.D. T h e s i s , U n i v . o f C a m b r i d g e , (1957).

28. P o w e l l , D. B., a n d S h e p p a r d , N.: J . Chem. S o c . (1956),
3108.
29. S v a t o s , G. F.', Sweeny, D. M. , M i z u s h i m a , S., C u r r a n , C. ,
a n d Q u a l g i a n o , J . V.,: J . A m e r . Chem. S o c . (1957),
22., 3313.
30. W a r d l a w , W., a n d Webb, H. W.s J . Chem. S o c . (1930), 2100.
31. T a u b e , H. , Chem. R e v s . (1952), ip_, 69.
32. P o w e l l , D. B., a n d S h e p p a r d , N.r J . Chem. S o c . (1959),
791.
33. W i l l a r d , H. H., a n d W i n t e r , 0. B.: I n d . E n g . Chem. A n a l .
E d . (1933), 5, 7.
34. P a u l i n g , L.: The N a t u r e o f t h e C h e m i c a l B o n d . r d . e d . ,
3

C o r n e l l , (i960).