Quinquecovalent Phosphorus Compounds

BY C. D. HALL

1 I n t r o d u c t i o n

I n t e r e s t i n h y p e r v a l e n t ( f i v e - and s i x - c o - o r d i n a t e d )

phosphorus compounds c o n t i n u e s a t t h e same l e v e l a s i n t h e

p r e v i o u s two y e a r s w i t h t h e m a j o r i t y of work f o c u s s e d on

monocyc l i c and b i c y c l i c p h o s p h o r a n e s . T h e r e have been no r e v i e w s

d e v o t e d s p e c i f i c a l l y t o phosphoranes b u t a s u r v e y of t h e pho to -

c h e m i s t r y of o rganophosphorus compounds' c o n t a i n s a s h o r t s e c t i o n

on p e n t a c o - o r d i n a t e d s p e c i e s . I t is i n t e r e s t i n g t o n o t e t h a t

k i n e t i c and s t e r e o c h e m i c a l s t u d i e s of f i v e - o r six-membered oxa-

and t h i a s i l a c y c l o a l k a n e s 2 have r e v e a l e d a number of a n a l o g i e s

be tween d i s p l a c e m e n t r e a c t i o n s a t s i l i c o n and phosphorus , i n c l u d i n g

t h e f o r m a t i o n of p e n t a c o - o r d i n a t e i n t e r m e d i a t e s .

2 S t r u c t u r e , Bonding, and L igand R e o r g a n i z a t i o n

An X-ray a n a l y s i s of t h e 2-hydroxyphenylenespirophosphorane

(1) r e v e a l e d a n e a r t b p c o n f i g u r a t i o n [0(1)-P-0(3) = 177.7OI

and a weak i n t e r a c t i o n be tween t h e phosphorus atom and t h e

p h e n o l i c h y d r o x y l g r o u p . S t r u c t u r a l a n a l y s i s of phosphoranes ( 2 )

and (3) show t b p c o n f i g u r a t i c m s w i t h d i s t o r t i o n s a l o n g t h e B e r r y

c o o r d i n a t e t o w a r d s s p s t r u c t u r e s of 21 .5% ( 2 a ) , 2 1 . 2 % ( 2 b ) and

19.1% (3). The s l i g h t l y g r e a t e r d i s t o r t i o n i n ( 2 ) is a t t r i b u t e d

t o a combina t ion of e f f e c t s i n c l u d i n g t h e s h o r t i n t r a m o l e c u l a r

c o n t a c t of O ( 1 ) w i t h C ( 1 3 ) , t h e i n t e r m o l e c u l a r N-H.*.*-O(l) hydrogen bonds (be tween 2 a and 2 b ) and e l e c t r o n i c e f f e c t s

r e s u l t i n g f rom t h e p r e s e n c e i n t h e a p i c a l p o s i t i o n of a donor atom,

N(1), which r e s u l t s i n an u n u s u a l l y l o n g P-0 a p i c a l bond of 182 pm. 4

0 The cyc lophosphorane ( 4 ) reacts w i t h d i b o r a n e a t 0 C t o

p roduce t h e bis(borane)cyclenphosphorane ( 5 ) i n which t h e a r r a n g e -

ment of atoms a round phosphorus is t h a t of a t b p d i s p l a c e d o n l y

10'.4% t o w a r d s t h e sp s t r u c t u r e . 5 The a p i c a l P-N bonds at

187.2 pm f o r P-N(1) and 186.4 pm f o r P-N(3) are t h e l a r g e s t y e t

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2: Quinquecovalen f Phosphorus Compounds 5 1

123 4'

R I

/N\ a; R = Me P, 7 1 3 CI

b; R = Ph N

(6a-c)

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52 Organophosphorus Chem is! ry

r e p o r t e d and these are compensa ted by t h e s h o r t e s t P-N e q u a t o r i a l

bonds of 1 6 4 . 5 pm f o r N(2) and 1 6 5 . 4 pm f o r N ( 4 ) . The P-H bond i s

a lso s h o r t a t 1 2 5 pm.

E l e c t r o n d i f f r a c t i o n h a s been u s e d t o d e t e r m i n e t h e gas -phase

s t r u c t u r e of F3P(NH2)2 which h a s a t b p c o n f i g u r a t i o n w i t h t h e

n i t r o g e n atoms occupy ing e q u a t o r i a l s i t e s and t h e p l a n e s o f t h e

NH2 g r o u p s p e r p e n d i c u l a r t o t h e e q u a t o r i a l p l a n e of t h e m o l e c u l e . 6

The two-fo ld t o r s i o n a l b a r r i e r of t h e NH2 g r o u p s , as o b t a i n e d f rom

t h e t o r s i o n a l a m p l i t u d e , is ca. 1 3 k c a l mol - I i n good agreement w i t h

n . m . r . measu remen t s .

q u e n c i e s and times of s p i n - l a t t i c e r e l a x a t i o n of t h e 35Cl n u c l e i i n

t h r e e c r y s t a l l i n e d i a z a d i p h o s p h e t i d i n e s (6a -c ) showed i n t r a m o l e -

c u l a r exchange of a p i c a l and e q u a t o r i a l c h l o r i n e atoms (I>.

r e a r r a n g e m e n t s of t h e p s e u d o r o t a t i o n a l t y p e ) w i t h a c t i v a t i o n e n e r -

g i e s of 25 .0 ( 6 a ) , 1 5 . 6 ( 6 b ) , and 2 1 . 0 ( 6 c ) k c a l m o l - l .

An i n g e n i o u s a p p l i c a t i o n of l80 i s o t o p i c s h i f t s on 31P n . m . r .

A s t u d y 7 of t h e t e m p e r a t u r e dependence of t h e n . q . r . f r e -

s p e c t r a h a s e s t a b l i s h e d d i f f e r e n t i s o t o p i c s h i f t s f o r a p i c a l and

e q u a t o r i a l oxygen atoms which may b e u s e d t o f o l l o w l i g a n d r e o r g a n -

i z a t i o n by means of v a r i a b l e t e m p e r a t u r e n . m . r . 8 F o r i n s t a n c e , t h e

31P n . m . r . s p e c t r u m of t h e s i n g l y l 8 0 - 1 a b e l l e d ( 0 ) phosphorane ( 7 )

a t O°C shows t w o p e a k s which coalesce a t 19OC l e a d i n g t o a agf v a l u e f o r t h e p s e u d o r o t a t i o n a l c o n v e r s i o n of ( 7 a ) t o ( 7 c ) v i a ( 7 b )

of 1 6 . 1 k c a l m o l - l .

d epends upon t h e s - c h a r a c t e r of t h e bond be tween phosphorus and t h e

i s o t o p e , t h e s u g g e s t i o n is made t h a t i t may u l t i m a t e l y b e p o s s i b l e

t o c o r r e l a t e i s o t o p i c s h i f t s w i t h geomet ry ( t b p 1 ) s . s ~ ) w i t h i n a

g i v e n t y p e o f phosphorane .

Assuming t h a t t h e s i z e of t h e i s o t o p i c s h i f t

3 P h o s p h o r a n e s C o n t a i n i n g a P-H Bond

T r i a l k y l t h i o p h o s p h i t e s ( 8 ) react w i t h c a t e c h o l ( 9 ) i n a 1 : 2

molar r a t i o t o p r o d u c e t h e s p i r o p h o s p h o r a n e ( 1 0 ) w i t h 631P = -21

p .p .m. I n a 1 : 3 molar r a t i o i n t h e p r e s e n c e of m i n e s however ,

h e x a c o - o r d i n a t e ammonium p h o s p h a t e s ( 1 1 , 631P = -87 p . p . m . ) are

o b t a i n e d i n 64% y i e l d . 9

The s t a b i l i t y of phosphoranes c o n t a i n i n g t w o f u s e d f i v e -

membered r i n g s h a s been e x p l o i t e d i n a k i n e t i c s t u d y of t h e reac- t i o n of t h e b i c y c l i c a m i d o p h o s p h i t e ( 1 2 ) w i t h t - b u t a n o l . "

f o r m a t i o n of (13) w a s s e c o n d - o r d e r o v e r a l l , showed a d e u t e r i u m

i s o t o p e e f f e c t kH/gD = 2 . 3 - 2 . 6 , w i t h A$ = 6 . 2 k 1 . 4 k c a l m o l - ' and AS-f = -50 .9 5 4 . 8 ca l m o l - ' K - l and w a s s t e r e o s p e c i f i c .

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2: Quinquecovalent Phosphorus Compounds 53

+

- ( B = bast)

B U ~ O H

H

a"'"'"JFJ 0' '0

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54 Organophosphorus Chemistry

r a t e was a l s o augmented ( a l b e i t o n l y s l i g h t l y ) by a d d i t i o n of

p y r i d i n e and t h e a u t h o r s i n t e r p r e t t h i s d a t a i n terms of a r a p i d ,

r e v e r s i b l e p r o t o n a t i o n of t h e amidophosph i t e f o l l o w e d by a s l o w ,

s t e r e o s p e c i f i c a t t a c k of t h e a l c o h o l a t e i o n ( e q n . 1 ) . I t is

ROH + :Pf k -- 1

p o s s i b l e , however , t h a t t h e a d d i t i o n of p y r i d i n e m e r e l y o f f e r s a

g e n e r a l b a s e - c a t a l y s e d pathway t o a s low a d d i t i o n of a p r o t o n t o

( 1 2 ) f o l l o w e d by a r a p i d c o l l a p s e of t h e i n t e r m e d i a t e i o n - p a i r

t o (13) v i a a r o u t e which k e e p s t h e t - b u t y l g roup as f a r a p a r t as

p o s s i b l e f rom t h e b u l k y p h e n y l ( a n d m e t h y l ) g r o u p s of t h e

a m i d o p h o s p h i t e .

S e v e r a l b i c y c l i c phosphoranes (e.g. 15) have been s y n t h e s i z e d

by r e a c t i o n s of t h e b i c y c l i c amidophosph i t e (14) w i t h a l c o h o l s ,

t h i o l s , amines , and phenols" and i n many cases t h e compounds are

s u f f i c i e n t l y s t a b l e t o b e i s o l a b l e by d i s t i l l a t i o n .

been s t u d i e d by 31P n . m . r . and t h e i r pKA v a l u e s i n DMF ( d e t e r m i n e d

p o t e n t i o r i l e t r i c a l l y ) are g e n e r a l l y lower t h a n t h o s e of c a r b o x y l i c

a c i d s (s. b e n z o i c a c i d ) i n t h e same s o l v e n t . 1 2 ' ,

been r e a c t e d w i t h ( i ) a l k y l h a l i d e s t o form p h o s p h o r a n e s (9. ZO), ( i i ) a z i d e s t o fo rm aminophosphoranes (21), and ( i i i ) ca rbon

d i s u l p h i d e t o form (22).

The B r o n s t e d a c i d i t i e s of p h o s p h o r a n e s of t y p e s (16-18) have

Anions d e r i v e d f rom phosphoranes (17), ( 1 8 ) , a n d ( 1 9 ) have

1 3

4 A c y c l i c Phosphoranes

The k i n e t i c s of t h e r e a c t i o n s of a c y c l i c p h o s p h i n e s ,

p h o s p h i n i t e s and p h o s p h o n i t e s w i t h d i e t h y l p e r o x i d e ( e q n . 2 )

have been r e p o r t e d t o g e t h e r w i t h t h e a c t i v a t i o n p a r a m e t e r s f o r

XJ = 1 and 2 and H a m m e t t p -va lues f o r n = 1 - 3.14 The d a t a

r e v e a l a b i m o l e c u l a r , non-po la r ( b i p h i l i c ) t r a n s i t i o n s t a t e f o r

e a c h r e a c t i o n w i t h p - v a l u e s d e r i v e d f rom l o g lf2 V 5 . u c o r r e l a t i o n s

which are v i r t u a l l y i n d e p e n d e n t of t h e n a t u r e of t h e t r i c o -

o r d i n a t e p h o s p h o r u s s p e c i e s .

Ab i n i t i o M.O. c a l c u l a t i o n s show t h a t a l o n e p a i r on oxygen - - which is a n t i p e r i p l a n a r t o t h e l o n e p a i r on phosphorus i n

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2: Quinquecovalent Phosphorus Compounds

A= a N > P / O 0

ROH _____)

(16)

(191

f17) R = Me

Et3N / Ph% 1

Noti / Me1 ______)

55 Me /

(20 1

- 1 ;rNHPh (21)

t ' HNEt3

(17) R = Me

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56 Organophosphorus Chemisky

p h o s p h i t e s , raises t h e e n e r g y of t h e s e m o l e c u l e s by 3.3 k c a l mol-'

r e l a t i v e t o a p h o s p h i t e c o n f o r m a t i o n w i t h no l o n e p a i r s

a n t i p e r i p l a n a r t o t h e p h o s p h i t e l o n e p a i r . 1 5

found (i?., s t a b i l i z a t i o n by a n t i p e r i p l a n a r l o n e p a i r s ) i n t h e

p r o t o n a t e d p h o s p h i t e b u t whereas t h e s t a b i l i z a t i o n i s c a l c u l a t e d

t o b e o n l y 1 k c a l mo l - l a t a P-H d i s t a n c e of 1 4 0 pm, t h e

s t e r e o e l e c t r o n i c s t a b i l i z a t i o n rises t o a maximum of

>.12 kca l m o l - l a t a P-H d i s t a n c e of Ca. 300 pm.

s t a t e s t a b i l i z a t i o n is proposed as t h e o r i g i n of t h e o ( - e f f e c t .

E x p e r i m e n t a l e v i d e n c e f o r t h i s h y p o t h e s i s is p r o v i d e d by a

c o m p a r a t i v e s t u d y of t h e r e a c t i o n of t r i e t h y l p h o s p h i t e (23) and 16 t h e b i c y c l i c p h o s p h i t e (26) w i t h e t h y l b e n z e n e s u l p h e n a t e ( 2 4 ) .

T r i e t h y l p h o s p h i t e reacts r a p i d l y t o g i v e p e n t a e t h o x y p h o s p h o r a n e

( 2 5 ) whereas (26) g i v e s n o r e a c t i o n even though t h e e x p e c t e d

phosphorane (27) c a n b e p r e p a r e d f rom ( 2 5 ) and t h e t r i o 1 (28)

by an exchange r e a c t i o n . Thus t h e l a c k of r e a c t i v i t y of ( 2 6 ) is due t o a k i n e t i c r a t h e r t h a n a thermodynamic b a r r i e r and t h e

r e s u l t s are i n t e r p r e t e d i n terms of t h e s t e r e o e l e c t r o n i c (N-) e f f e c t . The same p a p e r a s c r i b e s t h e o r d e r of r e a c t i v i t y of a

series of a l k y l p h o s p h i t e s towards 3-benzylidene-2,4-pentanedione t o a s imilar s t e r e o e l e c t r o n i c e f f e c t . The @ - e f f e c t may t o some

e x t e n t b e r e s p o n s i b l e f o r t h e enhanced r e a c t i v i t y o f a c y c l i c

p h o s p h i n i t e s and p h o s p h o n i t e s o v e r p h o s p h i n e s t o w a r d s d i e t h y l

p e r o x i d e ( a n d s e v e r a l o t h e r s u b s t r a t e s ) 1 4 b u t it canno t b e t h e

o n l y f a c t o r s i n c e i t i s w e l l e s t a b l i s h e d t h a t p h o s p h i n e s react

f a s t e r t h a n p h o s p h i n i t e s or p h o s p h o n i t e s i n n u c l e o p h i l i c d i s p l a c e -

ment r e a c t i o n s on a l k y l h a l i d e s .

p r e p a r e d and t h e i r 31P n . m . r . s p e c t r a r e c o r d e d .

e n e r g y r e l a t i o n s h i p was f o u n d be tween t h e 31P n . m . r . s h i f t o f many

of t h e p h o s p h o r a n e s and t h e p& of t h e c o r r e s p o n d i n g p h e n o l and

i n g e n e r a l , e l e c t r o n - w i t h d r a w i n g g r o u p s gave rise t o d o w n f i e l d

s h i f t s domina ted by e l e c t r o n e g a t i v i t y e f f e c t s b u t i n which

n-bonding c o n s i d e r a t i o n s a l so a p p e a r t o b e i m p o r t a n t .

(29-32) have been r e c o r d e d a t v a r i o u s t e m p e r a t u r e s and r e v e a l

t h a t t h e apical f l u o r i n e s are n o n - e q u i v a l e n t even at room t e m p e r a t u r e . A s t h e t e m p e r a t u r e was lowered t h e s p e c t r a showed

e v i d e n c e f o r t w o isomeric f o r m s , i n e a c h case a t t r i b u t e d t o

s l o w i n g of i n t e r n a l r o t a t i o n a b o u t t h e P-N bond.

The r e v e r s e i s

Hence t r a n s i t i o n -

A number of d i a r y l o x y t r i p h e n y l p h o s p h o r a n e s have been

A l i n e a r f r e e

17

The 19F and 31P n . m . r . s p e c t r a of f o u r f l u o r o p h o s p h o r a n e s

18

The a c c e p t o r p r o p e r t i e s of a series of a l k y l c h l o r o p h o s p h o r a n e s

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2: Quinqueco valen t Phosphorus Compounds

(EtO),P + 2 EtOSPh C5H12 -78 “c

F

Cki=: Me P

( 2 9 ) R = Ph (30) R = Me

(Et0)cjP + PhSSPh

( 2 5 )

OEt I

e 7 - O E t 0

F I 3

Me

(31) R = Ph ( 3 2 ) R = Me

57

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58 Organoph osp k orus Chemistry

RlrPC15-g ( w i t h R = Me, n = 1 or 2 and R = E t , ; = 1 or 2 ) towards

t h e Lewis b a s e s C1-, p y r i d i n e , 2 , 2 ' - b i p y r i d i n e and

1 , l O - p h e n a n t h r o l i n e , have been i n v e s t i g a t e d by 31P n . m . r .

Complex f o r m a t i o n w a s o b s e r v e d w i t h MePC14 and EtPClq ( a n d t h e i r

d e r i v a t i v e s ) b u t t h e di- and tetraalkylchlorophosphoranes showed

no e v i d e n c e of a c c e p t o r a b i l i t i e s .

19

The r e a c t i o n of phosphorus p e n t a c h l o r i d e w i t h cyc lohexene

g i v e s a m i x t u r e of tP~~8-1,2-dichlorocyclohexane ( 3 4 ) and

3 -ch lo rocyc lohexene ( 3 5 ) . The mechanism p r o p o s e d i n non-po la r

media (cg. benzene ) i n v o l v e s n u c l e o p h i l i c a t t a c k of t h e a l k e n e on

an e q u a t o r i a l c h l o r i n e atom of PC15 t o g i v e an i n t e r m e d i a t e

c h l o r o c y c l o h e x y l c a t i o n ( 3 3 ) f o l l o w e d by a d d i t i o n or

e l i m i n a t i o n , 2 0

F i n a l l y , a l t h o u g h n o t s t r i c t l y r e l e v a n t t o phosphorus

c h e m i s t r y , men t ion i s made h e r e of t h e p r e p a r a t i o n of p e n t a k i s -

( 2 , 2 , 2 - t r i f l u o r o e t h o x y ) a r s o r a n e ( 3 8 ) f rom t h e r e a c t i o n of ( 3 6 )

w i t h c h l o r i n e , p re sumab ly v i a d i s p r o p o r t i o n a t i o n of t h e i n t e r -

m e d i a t e (37) .21

( 3 8 ) showed no change s u g g e s t i n g t h a t , as p r e d i c t e d , t h e i n t r a -

m o l e c u l a r exchange h a s a low a c t i v a t i o n e n e r g y . R e a c t i o n of (38) w i t h l i t h i u m t r i f l u o r o e t h o x i d e gave a material w i t h n . m . r . d a t a

c h a r a c t e r i s t i c of t h e a r s e n a t e ( 3 9 ) .

The v a r i a b l e t e m p e r a t u r e I9F n . m . r . s p e c t r u n of

22

5 R i n g - c o n t a i n i n g Phosphoranes

5 . 1 Monocyc l i c P h o s p h o r a n e s . - H e x a f l u o r o a c e t a n e reacts w i t h a se r ies of y l i d s ( 4 0 ) a t -6OOC i n e t h e r t o g i v e q u a n t i t a t i v e

y i e l d s of t h e p h o s p h o r a n e s ( 4 1 ) which decompose on h e a t i n g t o

150° v i a an anomalous ( n o n - W i t t i g ) r o u t e t o fo rm ( 4 2 ) w i t h

p r e s e r v a t i o n of t h e P-C bond . 23

( 4 3 ) however , decomposes i n a c c o r d a n c e w i t h t h e no rma l c o u r s e of

t h e W i t t i g r e a c t i o n t o form ( 4 4 ) and ( 4 5 ) .

The ana logous methoxy phosphorane

T h r e e p h o s p h o r a n e s (48-50) a re g v a i l a b l e f rom t h e r e a c t i o n

of e i t h e r Et2POCH(CF3)2 or Et2PCl w i t h h e x a f l u o r o a c e t o n e o r d i l i t h i u m p e r f l u o r o p i n a c o l a t e . 2 4

phosphorane (50) is n o t c o n v e r t e d t o ( 4 8 ) on h e a t i n g .

Somewhat s u r p r i s i n g l y ,

The a c t i v a t i o n p a r a m e t e r s f o r t h e u n c a t a l y s e d l o s s of oxygen

f rom t r i p h e n y l p h o s p h i t e o z o n i d e ( e q n . 3 ) i n t o l u e n e , c h l o r o -

benzene , o r a c e t o n i t r i l e are a l l v e r y s i m i l a r w i t h

gA = 1 9 . 4 - 2 0 . 1 k c a l m o l - ' and l o g A = 13.5 - 1 3 . 6 ( A i n s - l ) ,

(Ph0)3P03 - (Ph0)3P0 + O2 (3)

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2: Quinquecovalent Phosphorus Compounds 59

Cl I

8ut(R3 P=CHR2 + (CF3 12 CO

(40) R’ = But or NEt2 R 2 = H or Me

(39) 6 7 5 A ~ = 190.3

- + 2 CF3CHzO Li

1 150°c

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60 Organophosphorus Chemistry

The d a t a , t o g e t h e r w i t h n . m . r . e v i d e n c e , l e a d t o t h e p r o p o s a l

of ozonide decomposi t ion by i r r e v e r s i b l e 0-0 bond s c i s s i o n t o

g i v e a s i n g l e t b i r a d i c a l which undergoes immediate B-sciss ion

t o phosphate and s i n g l e t oxygen.25

p a r t i c u l a r when t h e ozon ide is expec ted t o be i n h e r e n t l y s t a b l e ,

t h i s mechanism may be masked or ove r t aken by a second , p o s s i b l y

induced mode of decompos i t ion .

I n o t h e r c a s e s , and i n

S e v e r a l 2,4-dimethoxy-€J-substituted d i a z a d i p h o s p h e t i d i n e s ( 5 1 )

have been s y n t h e s i z e d and f u l l y c h a r a c t e r i z e d ; some of t h e s e

compounds (s, R = R ' = Me) show p romis ing i n s e c t i c i d a l

a c t i v i t y . 26

A m e c h a n i s t i c s t u d y of t h e r e a c t i o n s of t r i a r y l p h o s p h i n e s

w i t h t h e b i cyc loendoperox ides (52-54) t o form c y c l i c phosphoranes

( and t h e i r decomposi t ion p r o d u c t s ) r e v e a l s a series of

b i m o l e c u l a r r e a c t i o n s w i t h a c t i v a t i o n p a r a m e t e r s , s o l v e n t e f f e c t s

and H a m m e t t P-values i n l i n e w i t h a b i p h i l i c i n s e r t i o n

mechanism.27

s u b s t i t u e n t s i n t h e a r y l g roups on phosphorus which a g r e e s w i t h

Bsums ta rk ' s f i n d i n g s f o r (55 )28 b u t c o n t r a s t s w i t h t h e c o r r e l a t i o n

w i t h o-values found f o r d i e t h y l p e r o x i d e .

However, t h e r a t e s c o r r e l a t e w i t h t h e 0' v a l u e s of

14

I n a pape r d e a l i n g mainly w i t h p h o s p h i t e c h e m i s t r y , ( 5 6 )

is shown t o r e a c t w i t h c h l o r i n e t o g i v e t h e u n s t a b l e (57) which

(amongst o t h e r r e a c t i o n s ) d i s p r o p o r t i o n a t e s t o t h e t r i c h l o r o -

phosphorane (58 ) and t h e phospha te ( 5 9 ) . 29

The aminophosphi tes (60qb) r e a c t w i t h hexaf l u o r o a c e t o n e t o

g i v e t h e monocycl ic phosphoranes (61ap); compound (61b) is a l s o

o b t a i n a b l e from (60b) by r e a c t i o n w i t h c h l o r i n e fo l lowed by t h e

d i l i t h i u m s a l t of t h e p e r f l u o r o d i o l ( 6 2 ) .30

r e a c t i o n ( 6 0 b ) gave t h e a c y c l i c phosphorane ( 6 3 ) by r e a c t i o n w i t h

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

s u g g e s t t h a t t h e s e phosphoranes a r e n o t s u b j e c t t o l i g a n d

r e o r g a n i z a t i o n a t room t e m p e r a t u r e .

I n an ana logous

30

Phosphoranes c o n t a i n i n g a t h i o v i n y l goup ( 6 5 ) p r e p a r e d by

t h e c h l o r i n a t i o n of ( 6 4 ) , decompose on h e a t i n g t o a m i x t u r e of

( 6 6 ) and (67) and are of c o u r s e hydro lysed t o (68) .31

S e v e r a l monocycl ic t r i c o - o r d i n a t e phosphorus compounds w i t h

oxygen, n i t r o g e n , a n d s u l p h u r bound t o phosphorus have been

r e a c t e d wi th f l u o r o a l k y l benzenesu lphena te s and

3 , 4 - ( b i s t r i f l uo romethy l ) - 1 , 2 - d i t h i e t e n e and i n some c a s e s

(eg. 69-74) phosphoranes were formed and t h e i r s t r u c t u r e s and

s u s c e p t i b i l i t y t o l i g a n d r e o r g a n i z a t i o n s t u d i e d by v a r i a b l e

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2: Quinquecovalent Phosphorus Compounds 61

Et,PCI

LioCm(CF,), \

100 O C / 3h Et . . ~ ~ ~ ( c F 3 ) 2 H

CI Me

(47 1

_I__)

(CF3 12CHO' I

LiOCH(CF3)2

( 4 8 ) (49)

LiOCH(CF3)z I (46)

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62 Organophosphorus Chemistry

( 5 6 )

ICl2

( 5 7 )

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2: Quinquecovalent Phosphorus Compounds 63

(60) a; R = M e b; R = E t

(60b) + CI2 + LiOC(CF3)2C(CF3)20Li - (61b)

(62 )

(60b) + Cl2 + 2 LiOCH(CF3), d Et2NP[OCH(CF3)214

(63)

SR

P-S-C=CMe2 I

(64)

ao‘p40 0’ ‘S-C=CMq

(68)

0 CI SR CI s a a > P C l + Me,C-CSR I II

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64 Organophosphorus Chemistry

t e m p e r a t u r e n . m . r . 3 2 1 33

t o c o n v e r t ( 7 5 ) i n t o t h e p e n t a a l k o x y phosphorane ( 7 7 ) v i a t h e

mechanism shown.

T h e r m o l y s i s o f t h e y l i d ( 7 8 ) g i v e s e i t h e r ( 7 9 ) o r ( 8 0 )

depend ing upon t h e p e r i o d o f h e a t i n g , 3 4 and w h e r e a s ( 7 9 ) reacts

r e a d i l y w i t h me thano l ( t o form 8 1 ) o r w a t e r , ( 8 0 ) unde rgoes o n l y

h y d r o l y s i s . Mechanisms a r e p roposed f o r t h e f o r m a t i o n o f b o t h

p h o s p h o r a n e s .

I n o n e case an u n u s u a l r e a c t i o n o c c u r r e d

I n two r e l a t e d p a p e r s , t h e s y n t h e s i s of phosphoranes (eA. 8 3 )

f rom t h e a d d i t i o n o f p h o s p h i t e s ( 8 2 ) t o d i m e t h y l a c e t y l e n e d i -

c a r b o n a t e is d e s c r i b e d a n d t h e mechanism a n d s t e r e o c h e m i s t r y of 36 t h e s e r e a c t i o n s are d i s c u s s e d .

A d e t a i l e d 'H, 13C,and 31P n . m . r . s t u d y o f monocyc l i c

phosphoranes c o n t a i n i n g 1 I 2 - o x a p h o s ~ h o l e n i c ( 8 4 )

1 , 3 , 2 - d i o x a p h o s p h o l e n i c ( 8 5 ) a n d 1 , 3 , 2 - o x a z a p h o s p h o l e n i c ( 8 6 ) r i n g s

w i t h an a c y l (or a r o y l ) g r o u p a t p o s i t i o n 4 , l e a d s t o t h e

c o n c l u s i o n t h a t p h o s p h o r o t r o p i c t a u t o m e r i s m (s. 87-88) t a k e s p l a c e

be tween t h e two phosphorane s t r u ~ t u r e s ~ ~ , t h u s e q u i l i b r a t i n g Me a n d MeB on t h e n . m . r . time scale .

s u g g e s t s t h a t t h e open d i p o l a r form o f t h e s e p h o s n h o r a n e s makes

o n l y a minor c o n t r i b u t i o n t o t h e e q u i l i b r i u m m i x t u r e .

d e t e r m i n e d i n v a r i o u s s o l v e n t s by 300 MHz and 500 MHz 'H n .m . r .

I t i s shown by compar i son w i t h compounds s u c h as (90) where t h e

e n d o c y c l i c oxygen i s r e p l a c e d by CH2, t h a t l o w e r i n g t h e s o l v e n t

p o l a r i t y r e s u l t s i n r o t a t i o n a round C4 -C5

d r i v e n b y c h a r g e r e p u l s i o n be tween 01' and 05 ' .

I n h i b i t i o n o f p s e u d o r o t a t i o n i n monocyc l i c phosphoranes

(92-94) h a s been s t u d i e d b y m u l t i n u c l e a r n . m . r . and shown t o be

due t o s t e r i c i n h i b i t i o n by t h e t - b u t y l g r o u p s s i n c e (95) shows no

d e t e c t a b l e b a r r i e r t o l i g a n d r e o r g a n i z a t i o n . 39

sect i o n , t h e t h e r m o l y s i s of phosph( v ) o l e s ( e g . 9 6 ) g i v e s t h e

p h o s p h o l e d imer ( 9 8 ) v i a t h e i n t e r m e d i a t e p h o s p h i n i m i n e (971 .

A

E v i d e n c e is p r e s e n t e d which

I I

The C4 - C 5 c o n f o r m a t i o n o f compounds s u c h as ( 8 9 ) have been

I 1

t o w a r d s g (91) which is 38

F i n a l l y i n t h i s

40

5 . 2 B i c y c l i c a n d T r i c y c l i c P h o s p h o r a n e s . - The i n t r a m o l e c u l a r

a d d i t i o n o f t h e t r i m e t h y l s i l y l g r o u p t o t h e D=X bond (X = 0, NS02Ar,

or S ) of c y c l i c p h o s p h i t e esters (99) g i v e s a series of s p i r o -

p h o s p h o r a n e s ( 1 0 0 ) w i t h t h e p r o p e r t i e s of crown e t h e r s . 4 1

compounds show s e l e c t i v e complex f o r m a t i o n w i t h t h e l i t h i u m c a t i o n

b u t o n l y weak complexes w i t h Na', K', and C a 2 + .

These

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2: Quinquecovalent Phosphorus Compounds 65

Me Me

Me

(69) (70)

Me

I Me

(71)

CF~CHZOSP h

( 76) I

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66 Organophosphorus Chemistry

Me0 OMe

NMe I COzMe 0YH I O-P/ CONMe2 150 ‘C, 8 min

_______) /

‘CH(OMe)C02Me

MeOH ____)

(79) (81)

R’ :%*>P- 0 OMe

R’

+

C02Me I c

C

0 2 M e I

R‘OH - (62 ) R ’= H or Me (63) R2 = Me or Ph

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2: Quinquecovalent Phosphorus Compounds 67

MeACO MeB MeA COMeB

H "\ P /CHMe

Me Me

H *4c5, 50

(89) (90) (91)

0 R1

P- OR2

OR1

I I

(92) R' = R2 D CH,CF3

(93) R' = CH2CF3, R 2 = CH,CH3

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68 Organophosphorus Chemistry

P r o t o n n . m . r . s t u d i e s d e m o n s t r a t e t h a t i n t h e a c i d - c a t a l y s e d

h y d r o l y s i s of s p i r o p h o s p h o r a n e s ( 1 0 1 ) l i g a n d exchange via an

i n t e r m e d i a t e c a t i o n ( 1 0 2 ) o c c u r s l o 7 times f a s t e r t h a n h y d r o l y s i s ,

showing t h a t ( 1 0 2 ) h a s a l a r g e p r e f e r e n c e f o r r e a c t i o n w i t h i t s

i n t e r n a l h y d r o x y l g r o u p o v e r c a p t u r e by an e x t e r n a l water

m o l e c u l e . 42

E l e c t r o p h i l i c a t t a c k on t h e (viny1oxy)-spirophosphorane (103)

o c c u r s by 1 , 6 - a d d i t i o n t o g i v e ( 1 0 4 ) or ( 1 0 6 ) , t h e r e a c t i o n w i t h

bromine p r o c e e d i n g t h r o u g h t h e i n t e r m e d i a t e ( 1 0 5 ) which may b e

t r a p p e d w i t h m e t h a n o l t o form ( 1 0 7 ) . 43

Novel b i c y c l i c aminophosphoranes ( 1 1 0 ) which are c h i r a l a t b o t h

phosphorus ( * ) and ca rbon ( * ) are formed by t h e r e a c t i o n of ( 1 0 8 )

w i t h (109) and t h e aminophosphoranes may b e c o n v e r t e d t o d i a s t e r e o

meric p a i r s of rhodium c h e l a t e s (s. l l l a , b ) which i n t u r n may be

s e p a r a t e d by f r a c t i o n a l c r y s t a l l i z a t i o n f rom a c e t o n i t r i l e . 44

I n t e r e s t c o n t i n u e s i n t h e p r e p a r a t i o n of p h o s p h i n i m i n e s and

t h e i r d i m e r i z a t i o n t o b i c y c l o o r s p i r o p h o s p h o r a n e s . The r e a c t i o n s

of phosphoroisocyanitidites or d i p h e n y l p h o s p h i n o u s i s o c y a n a t e

( 1 1 2 ) w i t h s a l i c y l a l d e h y d e ( 1 1 3 ) g i v e b i c y c l i c phosphoranes ( 1 1 5 )

u i a ( 1 1 4 ) . 45

exchange r e a c t i o n t o g i v e ( 1 1 5 ) w i t h R=C2H50.

phosphoranes ( 1 1 8 ) a lso o r i g i n a t e f rom ( 1 1 2 , R=MeO) and

1,1,1,5,5,5-hexafluoro-2,4-pentanedione ( 1 1 6 ) v i a ( 1 1 7 ) .

With R=C1C2H40, t r e a t m e n t w i t h e t h a n o l r e s u l t s i n an

S t a b l e b i c y c l i c

46

F a c t o r s a f f e c t i n g t h e t endency of 2-alkoxy-2-( a r y 1 i m i n o ) -

1 , 3 , 2 - d i o x a p h o s p h o l a n e ( 1 2 0 ) , p r e p a r e d f rom ( 1 1 9 ) and a r y l a z i d e s ,

t o d i m e r i z e t o ( 1 2 1 ) h a v e been i n ~ e s t i g a t e d . ~ ~ I n g e n e r a l , i n t r o -

d u c t i o n of e l e c t r o n - w i t h d r a w i n g s u b s t i t u e n t s i n t o t h e a r y l g r o u p

or f o u r m e t h y l g r o u p s i n t o t h e d i o x a p h o s p h o l a n e r i n g , r e d u c e s

d i m e r i z a t i o n . The l a t t e r c o n d i t i o n lowers t h e i n d u c t i v e e l e c t r o n

a c c e p t o r c a p a c i t y of t h e r i n g oxygens and hence s h i e l d s t h e

phosphorus atom. Work i n t h e same area h a s shown t h a t N- (2 -az idoe thy l ) -

a l k y l a m i n e s ( 1 2 2 ) react w i t h c y c l i c phosphorus compounds ( 1 2 3 ) t o

form a m i x t u r e of t w o s p i r o p h o s p h o r a n e s ( 1 2 4 ) and ( 1 2 5 ) , t h e

l a t te r b e i n g o b t a i n e d f rom ( 1 2 4 ) by l o s s of m i n e f o l l o w e d by

d i m e r i z a t i o n of t h e i n t e r m e d i a t e c y c l i c phosph imide ( 1 2 6 ) f 8

p a p e r p o i n t s o u t t h a t loss of m i n e and d i m e r i z a t i o n c o u l d a l so

b e a c o n c e r t e d p r o c e s s .

The

The same a u t h o r s have shown t h a t whereas a z i d o a m i n e s ( s e e

above ) and a z i d o c a r b o x y l i c a c i d s ( 1 2 8 ) react w i t h t r i c o - o r d i n a t e

phosphorus ( e g . 1 2 7 ) t o f o r m c y c l i c p h o s p h o r a n e s ( e s . 1 2 9 ) ,

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2: Quinquecovalen f Phosphorus Compounds 69

Cpo I _,Ph

HN- P' I b P h

OMe

N-P-Ph

Q-. I ,dPh

(99) (100)

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70 Organophosphorus Chemistry

OCH=CH, I I Me Me

M e y ) \ p 4 0

Me 0’ ‘OCH-CHBr

J MeOH / E tgN \

+ BrCHZCHO

MeXO=p~xMs Me 0 I 0 Me

I I Me Me

(106 1

OMe

(107)

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2: Quinquecovalent Phosphorus Compounds 71

RZPNCO + o-HOCGH~CHO

(112) (113)

\

\ /

HN

I / " R 2 r c H

o+

(1151

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72

(112 1

+

F3 CC°CH“CCF3 II I 0 OH

\ o

F3c CH=CCF3 ,?’

I OH

Organophosphorus Chemisfry

y 3 f i

Hc/L‘o

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2: Quinquecovalent Phosphorus Compounds 73

R1NHCH2CH2N3 +

(122)

80 O C , - H2 I

"2 P-Ph + N3CR1R2C02H +

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74 Organophosphorus Chemistry

- N-(2 -az idoe thy l ) - amides ( 1 3 0 ) form p h o s p h i n i m i n e s (131) which may

d i m e r i z e t o s t a b l e phosphoranes ( 1 3 2 ) . 49 With a c y c l i c p h o s p h i n e s

(eg. Ph3P) and ( 1 3 0 ) t h e i n t e r m e d i a t e Dhosph in imines ( 1 3 3 )

decompose t o g i v e t r i p h e n y l p h o s p h i n e o x i d e and i m i d a z o l i n e s ( 1 3 4 ) .

o f t h e p h o t o l y s i s o f X5-phosphorus a z i d e s (135-138) . 50

d i f f e r e n t t y p e s o f r e a c t i o n were o b s e r v e d depend ing upon t h e

s u b s t i t u e n t s on phosphorus . For example , w i t h (135) a C u r t i u s -

t y p e r e a c t i o n gave ( 1 3 9 ) which d i m e r l z e d t o ( 1 4 0 ) ; w i t h ( 1 3 6 ) a

t a u t o m e r i c e q u i l i b r i u m t o ( 1 4 1 ) was f o l l o w e d by a C u r t i u s

r e a r r a n g e m e n t t o ( 1 4 2 ) and f i n a l l y , w i t h ( 1 3 8 ) t h e i n t e r m e d i a t e

n i t r e n e ( 1 4 3 ) a b s t r a c t e d p r o t o n s f rom t h e s o l v e n t ( b e n z e n e ) t o

form ( 1 4 4 ) .

The s c o p e of t h e C u r t i u s r e a c t i o n h a s been e x t e n d e d by a s t u d y

T h r e e

I n a c o n t i n u a t i o n o f e a r l i e r s t u d i e s , Denney Et a. h a v e

r e p o r t e d t h e f o r m a t i o n of a wide r a n g e of phosphoranes ( 1 4 9 a n d 150)

b y t h e r e a c t i o n o f b i c y c l i c t r i c o - o r d i n a t e nhosphorus compounds

( 1 4 5 ) and ( 1 4 7 ) w i t h a ser ies of s u b s t i t u t e d b e n z i l s ( 1 4 8 ) . 51J 52

Although t h e compounds a re t o o u n s t a b l e t o b e i s o l a t e d i n p u r e

form, t h e 31P and I 3 C n . m . r . s p e c t r a i n d i c a t e t h a t t h e y a r e a l l

t r u e p e n t a c o - o r d i n a t e s t r u c t u r e s . V a r i a b l e t e m p e r a t u r e n . m . r .

s t u d i e s showed c o a l e s c e n c e nhenomena i n a l l c a s e s e x c e p t f o r ( 1 4 9 )

w i t h X = p - N 0 2 , Y=H,and X,Y=p-N02. A l l t h e o b s e r v a b l e l i g a n d

r e o r g a n i z a t i o n p r o c e s s e s showed s imi l a r a c t i v a t i o n e n e r g i e s i n t h e

r e g i o n o f 11-12 k c a l mol-l .

6 Hexaco-o rd ina te Phosphorus Compounds

The r e a c t i o n o f fluorodiazadiphosphetidines ( 1 5 1 ) w i t h

a l c o h o l g i v e s t h e h e x a c o - o r d i n a t e d i a z a d i p h o s n h e t i d i n e (152) a n d

e i t h e r monoalkoxy ( 1 5 3 ) o r dialkoxydiazaphosphetidine (154'1

depend ing upon t h e molar r a t i o of r e a c t a n t s . 5 3 I n a r e l a t e d

s t u d y t h e r e a c t i o n o f (151) w i t h d r y hydrogen f l u o r i d e g a v e (152)

b u t w i t h t h e me thy l g r o u p r e p l a c e d b y o t h e r a l k y l g r o u p s ( e s . 155

w i t h R=sec-Bu o r t e r t - B u ) t h e p h o s p h e t i d i n e s t r u c t u r e (152) b r o k e

down t a form amine-phosphorus p e n t a f l u o r i d e a d d u c t s ( 1 5 6 ) . 54

The r e a c t i o n of N , N ' - d i s u b s t i t u e d N-ch lo roamid ines ( 1 5 7 ) w i t h

t r i c o - o r d i n a t e phosphorus compounds ( 1 5 8 ) p r o v i d e s a g e n e r a l r o u t e

t o t h e amidin ium c h l o r o p h o s p h a t e s ( 1 5 9 ) which are p o t e n t i a l l y i n

e q u i l i b r i u m w i t h t h e c y c l i c p h o s p h o r a n e s ( 1 6 0 ) . 55

g r o u p s (%. ~ CF3) on t h e ca rbon atom, b u l k y s u b s t i t u e n t s (R2,R3) on

t h e a m i d i n e t r i a d , e l e c t r o n - w i t h d r a w i n g s u b s t i t u e n t s on phosphorus ,

E l e c t r o n acceptor

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2: Quinquecovalent Phosphorus Compounds

Ph A Ph

(127 1 + P(3CHzCH2 NHCOR

I ( 1 3 0 ) CH,CH,NHCOPh

(132)

/ Ph

(131)

-N, JN] Ph3P + (130) Ph3P=NCH2CH2NHCOR + Ph3P0 + RC

'N H

(134) (133) R = Me, Ph, or CF3

N3

(135)

N3

(136)

(137) (138)

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76 Organophosphorus Chemistry

(140) cis + trons

(141) (142 1

i

(143)

PhH - Q- 0. 0 I

"""-b -- P-0

(144)

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2: Quinquecovalent Phosphorus Compounds 77

p; o;P + ( 1 4 8 )

( 1 4 7 )

m n = =/ 3,

+ n R ~ O H /N\

m F,P \ N /pF3

I R1

(151 1

Ar '

(149)

(152)

PF2 OR2 /N\

I R'

(153 1

I R'

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78 Organophosphorus Chemistry

and p o l a r s o l v e n t s a l l d e s t a b i l i z e t h e h e x a c o - o r d i n a t e s t a t e and

s h i f t t h e c h l o r o t r o p i c e q u i l i b r i u m t o w a r d s ( 1 6 0 ) .

F i n a l l y n . m . r . s t u d i e s of (161) r e v e a l a h i g h a c t i v a t i o n

b a r r i e r o f 23 .6 k c a l mol-' f o r l i g a n d r e o r g a n i z a t i o n which is

t h o u g h t t o p r o c e e d v i a a r e g u l a r n o n - d i s s o c i a t i v e mechanism

i n v o l v i n g t h e s i m u l t a n e o u s change i n p o s i t i o n of a l l f o u r f l u o r i n e

a t oms. 56

H R \;/

(155) R =Bus or 6"'

R * I

R'- C /NC1 + CIPR4R5

'NR3 (158)

(157 1

Me I N

P h - C K ,PF4 \-

N

R2

2 HF ___)

R'

(159)

I Me

(161 1

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2: Quinqueco valen t Phosphorus Compounds 79

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12 13 14 15 16 17 18 19 20

21 22

23 24

25

26 27 28

29 30

31

32 33 34 35 36 37

38

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