Pentaco-ordinated and Hexaco-ordinated Corn pou nds

BY C. D. HALL

1 I n t r o d u c t i o n . - The y e a r h a s been one of c o n s o l i d a t i o n w i t h par-

t i c u l a r emphasis once a g a i n on t h e p r e p a r a t i o n and p r o p e r t i e s of

phosphoranes i n c o r p o r a t i n g small ( f o u r - and five-membered) r i n g s . An e x c e l l e n t r ev iew h a s appea red on t h e t h e r m o l y s i s of pen taco - o r d i n a t e d phosphorus h e t e r o c y c l e s ' and r ev iews on phosphor- adamantanes2 and n o n - b i o l o g i c a l a s p e c t s of 31P n . m . r . 3 , b o t h c o n t a i n s e c t i o n s d e a l i n g w i t h p e n t a c o - o r d i n a t e d and , i n t h e l a t t e r r e f e r e n c e , hexaco-o rd ina ted phosphorus compounds. I n a d d i t i o n t h e whole of Phosphorus and S u l f u r , V o l . 18, is devo ted t o a b s t r a c t s of p a p e r s p r e s e n t e d a t t h e l a s t I n t e r n a t i o n a l Confe rence on Phosphorus Chemistry ( N i c e , 1983) and i n c l u d e s

numerous c o n t r i b u t i o n s on h y p e r v a l e n t phosphorus compounds . 4

On t h e t h e o r e t i c a l f r o n t , e x t e n s i v e ab i n i t i o c a l c u l a t i o n s y i e l d e d a d e t a i l e d mechanism f o r Ber ry p s e u d o r o t a t i o n i n PF5 for which a b a r r i e r of 16 2 2 k J mol-'(3.8 2 0.5 k c a l mol-') was

o b t a i n e d . I n a d d i t i o n a comple t e q u a d r a t i c f o r c e f i e l d w a s c a l c u l a t e d which gave e x c e l l e n t agreement between c a l c u l a t e d and obse rved v i b r a t i o n a l f r e q u e n c i e s .

( X % X s , X = H,F, o r C l ) r e v e a l e d t r i g o n a l b i p y r a m i d a l s t r u c t u r e s w i t h t h e u n p a i r e d e l e c t r o n i n an a p i c a l p o s i t i o n , i n c o n t r a s t t o C2v s t r u c t u r e s where t h e odd e l e c t r o n w a s e q u a t o r i a l . The same p a p e r shows t h a t t h e o p t i m i z e d C_4v phosphorane r a d i c a l an ion (PF5-) is o c t a h e d r a l w i t h t h e u n p a i r e d e l e c t r o n a c t i n g as a l i g a n d . C a l c u l a t e d i s o t r o p i c h y p e r f i n e c o u p l i n g c o n s t a n t s were i n good agreement w i t h t h e expec ted v a l u e s .

2 S t r u c t u r e and Bonding. - A s i n g l e - c r y s t a l X-ray a n a l y s i s of t h e monocycl ic phosphorane (1) r e v e a l e d a t b p geometry w i t h a 27.2% d i s t o r t i o n a l o n g t h e B e r r y c o o r d i n a t e towards r p and t h e five-membered r i n g e s s e n t i a l l y a p i c a l - e q u a t o r i a l ( w i t h 01-P-03 = 87.1°)7.

5

Ab i n i t i o c a l c u l a t i o n s on v a r i o u s c3v phosphorany l r a d i c a l s

6

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52 Organophosphorus Chemistry

0 0

-0 -0- +

2Et3NH

The c r y s t a l s t r u c t u r e of t h e t r ie thylammonium s a l t ( 2 ) of t h e bis-hydroxyspirophosphorane p r e p a r e d from PC13 and t a r t a r i c a c i d r e v e a l s t h a t t h e compound c o n s i s t s of two t r i g o n a l b i p y r a m i d s abou t t h e two phosphorus atoms which are connec ted by t h e t a r t a r i c a c i d l i g a n d s . The d ioxaphospho lane r i n g s a r e p l a n a r and t h e e x o c y c l i c P-0- bonds are s h o r t ( a t 150 and 148 pm) i n l i n e w i t h t h e h igh Br4ns ted a c i d i t y of t h e bis-hydroxyphosphorane p r e c u r s o r .

8

CI 0 - II

OCCF3 II 0 172

( 3 )

Although n o t d i r e c t l y r e l e v a n t t o phosphorus , some i n t e r e s t i n g s t r u c t u r a l d a t a has been r e p o r t e d on p e n t a v a l e n t organobismuth compounds . The 8 -hydroxyqu ino l ine d e r i v a t i v e ( 3 ) of t r i p h e n y l - b i smuth d i c h l o r i d e w a s e s s e n t i a l l y a t b p s t r u c t u r e w i t h t h e t h r e e pheny l rings e q u a t o r i a l and t h e n i t r o g e n atom d i r e c t e d towards t h e

9

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 53

c e n t r a l b i s m u t h atom. I n t h e d i p h e n y l bis(trif1uoroacetato)bis- m u t h a t e a n i o n ( 4 ) t h e t w o t r i f l u o r o a c e t a t e g r o u p s were f o u n d t o b e a p i c a l l e a v i n g t h e two p h e n y l g r o u p s t o g e t h e r w i t h t h e l o n e p a i r

( p h a n t o m l i g a n d ) e q u a t o r i a l i n t h e s l i g h t l y d i s t o r t e d (0-Bi-0 = 172') t r i g o n a l b i p y r a m i d . 3 P h o s p h o r a n e s t h a t c o n t a i n a P-H Bond. - A p p l i c a t i o n o f low- t e m p e r a t u r e 31P n.m. r , t e c h n i q u e s h a s shown t h a t t h e h y d r i d o - p h o s p h o r a n e ( 6 ) is a n i n t e r m e d i a t e i n t h e i n t r a m o l e c u l a r t r a n s -

e s t e r i f i c a t i o n of ( 5 ) t o (71~ ' .

A

( 5 )

The ra te of i n t e r c o n v e r s i o n i s c a t a l y s e d by b a s e w h i c h m i m i c s t h e role o f H i s t i d i n e 1 2 a n d d i s t i d i n e 113 i n t h e a c t i v e s i t e of RNA-

ase d u r i n g t h e h y d r o l y s i s of r i b o n u c l e i c a c i d s , c.f. ( 8 ) w i t h

( 9 ) - ( 1 1 ) .

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54 Organophosphorus Chemisq

base I

B H-

(8 1

(10)

B...

8. ..

( 9 )

( 1 1 1

R e a c t i o n s of t h e h y d r o p h o s p h o r a n e ( 1 2 ) are s u m m a r i z e d i n

Scheme 1 f r o m w h i c h i t may be s e e n t h a t t h e compound is a u s e f u l

p r e c u r s o r t o n u m e r o u s p e n t a c o - o r d i n a t e d s t r u c t u r e s ( 1 3 - 1 9 ) . 4 A c y c l i c P h o s p h o r a n e s . - A c o m b i n a t i o n o f i . r . s p e c t r a a n d 31P/19F n . m . r . d a t a h a s shown t h a t t h e t e t r a p h e n y l f l u o r o p h o s p h o r a n e g e n e r a t e d from ( 2 0 ) ( 2 1 ) may e x i s t as t h e m o n o m e r i c i o n i c form ( 2 2 ) , t h e molecular f o r m ( 2 3 ) , o r t h e d i m e r ( 2 4 ) 1 2 .

T h e r e a c t i o n of r e d p h o s p h o r u s w i t h a l k y l h a l i d e s i n t h e

11

p r e s e n c e of 1 . 5 -+ 2 . 5 moles of i o d i n e g a v e d i a l k y l p o l y i o d o -

p h o s p h o r u s compounds R P I ( 2 5 ) w i t h n = 4 or 5 . On d i s s o l u t i o n

i n a c e t o n i t r i l e s o l u t i o n , ( 2 5 ) w i t h R = M e o r E t , d i s s o c i a t e d t o

13 2 n _

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 55

( 1 4 ) (13)

Me2S0

(1 5 )

(17) ( 1 2 1

(18)

where R = CF,

+ Me3PH

R 2

(19)

(16 )

Scheme 1

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56 Organophosphorus Chemistry

t h e c o r r e s p o n d i n g dialkyltriiodophosphoranes ( 2 6 ) .

+ * Ph,P Ph4PF2 + 300 OC Cold trap Ph,P HF2 - Ph4PF

(21 1 (23) (24) 31

\I 817crn” (P-F) 8 P, +22.5, -1 5.2

R 2 P * s MeCN - - R f I , t I,

(25) ( 2 6 ) R = M e or Et

A f u r t h e r r e p o r t h a s a p p e a r e d on t h e p r e p a r a t i o n of phos- p h o r a n e s ( 2 9 ) from t h e r e a c t i o n of h e x a f l u o r o i s o p r o p o x y benzene-

14 s u l p h e n a t e ( 2 7 ) w i t h p h o s p h i n i t e s ( 2 8 a ) and p h o s p h o n i t e s ( 2 8 b ) . With p h o s p h i t e s (3 . 30) t h e i n t e r m e d i a t e t h i o p h o s p h o r a n e (31) was i s o l a t e d i n 64% y i e l d ( 6 31P = 5 4 . 0 ) .

19F n.m. r . s p e c t r a showed t h a t l i g a n d r e o r g a n i z a t i o n w i t h i n t h e s e

a c y c l i c p h o s p h o r a n e s w a s i n f l u e n c e d by s t e r i c f a c t o r s .

V a r i a b l e t e m p e r a t u r e

2PhSOCH(CF3)2 + Ph, P[OCH(CF3),13-n - PhnP[OCH(CF3)21 5-n

( 2 7 ) ( 2 9 )

( 2 7 1 + P[OCH(CF,),I, - PhSP[OCH(CF,)214

(30) ( 3 1 )

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 57

F u l l d e t a i l s have a p p e a r e d on t h e p r e p a r a t i o n of p e n t a c o - o r d i n a t e d p h o s p h o r u s compounds by n u c l e o p h i l i c a d d i t i o n of

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 t o a c t i v a t e d d o u b l e bonds i n t h e p r e s e n c e of a l c o h o l s and p h e n o l s . Many of t h e s e r e a c t i o n s p roduced h i g h y i e l d s of a c y c l i c p h o s p h o r a n e s (e.g. 32 or 3 3 ) b u t i n a d d i t i o n , d i o l s and c a t e c h o l s g a v e m o n o c y c l i c p h o s p h o r a n e s (e.g. 34 or 35 r e s p e c t i v e l y ) and u s e of a c y c l i c p h o s p h i n o t h i o i t e ( 3 6 ) g a v e t h e s p i r o p h o s p h o r a n e ( 3 7 ) .

15

P h,P (OE t 1 , C H , CH, CN

(32)

PCH,CH, C0,Et (>C ( 3 4 )

PhP(OEt),CH,CH,CO,Et

( 3 3 )

fi O\ PCH,CH,CN ph But 0' b h

( 3 5 )

+ CH,=CHCO,Et P

Me

(36 1

C0,Et

(37 )

I n an e x t e n s i o n of t h e e l e g a n t work begun by Westheimer",

Queen e t a l . h a v e s t u d i e d t h e k i n e t i c s of h y d r o l y s i s of ( 3 8 ) and (39) i n aqueous d i o x a n 1 7 . h y d r o l y s i s of ( 3 9 ) w a s -188 J m o l - ' K - l ( -42 c a l mol-' K- l ) and t h e c o r r e s p o n d i n g e n t h a l p y of a c t i v a t i o n w a s 2 2 . 5 k J mol- ( 5 . 0 k c a l rnol-l), which i s l o w f o r a r e l a t i v e l y s l o w r e a c t i o n .

The e n t r o p y of a c t i v a t i o n fo r t h e

1

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58 Organophosphorus Chemistry

( 3 8 )

OH

0 CF CF II 1 3 1 3

Ph (RO) P 0 C -COH I I CF3 CF3

Trle d a t a s u g g e s t a m u l t i s t e p p r o c e s s i n v o l v i n g an i n i t i a l e q u i -

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

an ism i n v o l v e s f o r m a t i o n of a s i x - c o o r d i n a t e d i n t e r m e d i a t e (g. 40) f o l l o w e d by l o s s of a l c o h o l ( o r p h e n o l ) t o g i v e ( 4 1 ) and t h e n ( 4 2 ) . 5 Four-membered-ring P h o s p h o r a n e s . - The cis- and t r a n s 4 x a p h o s - p h e t a n s ( 4 3 and 44 r e s p e c t i v e l y ) have been o b s e r v e d i n t h e W i t t i g r e a c t i o n by h i g h f i e l d ( 1 4 5 . 8 MHz) 31P n . m . r . s p e c t r o s c o p y a t -780C18. l ower f i e l d ( -61 .4 and -59.7 p . p . m . ) t h a n t h e t r a n s ( a t -63.8.and - 6 4 . 3 p . p.m. ) . t o z and E_ a l k e n e s , b u t w h e r e a s case ( b ) g a v e an a l k e n e r a t i o which r e f l e c t e d t h e oxaphosphe tan r a t i o , case ( a ) gave a lower Z_/g r a t i o (1 .5 ) t h a n i n t h e o r i g i n a l oxaphosphe tan ( 3 . 8 ) i m p l y i n g e q u i l i - b r a t i o n o f t h e p h o s p h o r a n e s a t a ra te which was c o m p e t i t i v e w i t h

t h e ra te of d e c o m p o s i t i o n . Case ( c ) g a v e a s i n g l e oxaphosphe tan ( t h e cis i s o m e r , 6 31P = 6 1 . 9 p . p . m . ) and a 9 6 : 4 , z : E r a t i o of

a l k e n e s .

I n cases ( a ) and ( b ) t h e cis isomer w a s o b s e r v e d a t

On warming t o E. -30° b o t h m i x t u r e s decomposed

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 59

1 Ph,P=CHR + R'CHO

R

Ph,PO

(43a-c ) (44a - c )

a ; b;

A C ; 1 + d #,2

Z

R' = Pr", R2= Ph

R1 = Me, R 2 = Ph

R~ = Pr", R' = c,H,,

Ph,PO

I A

+ 6 Xd E

O x i d a t i v e a d d i t i o n of ozone t o a series of p h o s p h i t e s g i v e s phosphoranes c o n t a i n i n g t h e t r i o x a p h o s p h e t a n r i n g ( e . - g . 45-47)". With p h o s p h i t e s d e r i v e d from 8 -hydroxyqu ino l ines however, t h e r e s u l t a n t ozon ide (e-g. 48) h a s phosphorus i n t h e hexaco-o rd ina te s ta te . Decomposition of t h e compounds t o phospha te s and s i n g l e t oxygen is dependent upon s t r u c t u r e and t h e s o l v e n t , w i t h ra tes d e c r e a s i n g i n t h e o r d e r ( 4 7 ) > ( 4 5 ) > ( 4 6 ) > ( 4 8 ) and more p o l a r s o l v e n t s a f f o r d i n g g r e a t e r s t a b i l i t y t o ( 4 8 ) . S t e r e o c h e m i s t r y

a t phosphorus i s p r e s e r v e d d u r i n g t h e io rma t io i i and the aecompo- s i t i o n of t h e o z o n i d e s .

R e a c t i o n of t h e phosphetan ( 4 9 ) w i t h 2,3-dioxabicyclo[2.2.1]- h e p t a n e (50) gave a m i x t u r e of two, k i n e t i c a l l y d i s t i n g u i s h a b l e , d i a s t e r e o i s o m e r i c phosphoranes ( 5 1 and 5 2 ) . The s t r u c t u r e s w e r e

a s s i g n e d by 1 3 C n .m. r . s p e c t r a which d i d n o t e x c l u d e t h e p o s s i b i l i t y o f t r i g o n a l b i p y r a m i d a l s t r u c t u r e s w i t h t h e phenyl g roups cis or t r a n s t o t h e b r i d g e methylene g roups . Hea t ing t h e m i x t u r e t o 145' r e s u l t e d i n decompos i t ion of t h e phosphoranes b u t t h e r e w a s no i n d i c a t i o n of any i n t e r c o n v e r s i o n of i somers by p s e u d o r o t a t i o n .

2 0

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60 Organophosphorus Chemistry

OC,H,X I

/O\ (P-XC H 0) P

\o,o

31 ( 4 5 ) 8 P, ca.-62

R '

( 4 7 ) a3'P, CU. - 56

( 4 6 ) S3'P, CU.-36

( 4 8 )

Me

+ +

'M e

( 5 2 )

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 61

The use of an electron-accepting trihalogenomethyl group (R = CF3 or CCl,) in compounds of type (53) provides the first example of chlorotropic tautomerism with an accompanying change in the coordination of the phosphorus atom from VI (in 53) to V (in 55) via the transition state ( 5 4 ) . The position of the tautomeric equilibrium shifts towards (55) as the electron with- drawing power of R increases, as the polarity of the solvent decreases, and as the temperature rises . 21

Me

(53 )

R = CF, or CCl,

g3'P, -199 or -52

$1.

R-C; ,bCl, . = . *

\N% N Me \

L Me

(54)

(55 1

R = CF3 or CCI,

g3'P, -193 or - 5 0

C6F,N -PCl,

6 5 C1,P-NC F

- I I + PCI, - N C l

( 5 6 ) ( 5 7 )

Interest in the dimerization of iminophosphoranes continues and examples include the reaction of the chloroiminohexadiene ( 5 6 )

with PC13 to produce (57) ,22 the reaction of phosphites (ex. 58)

with phenyl azide to form (60)% (59)F3 and the synthesis (as shown) of a rare type of compound (62 ) containing both pentaco- ordinated phosphorus and an azido group . The products of the reaction between phosphoramidites ( 6 3 ) and an azide (64 ) depend upon the size of the exocyclic substituent. pentaco-ordinated structures ( 6 5 ) predominate but with R1= Pri ,

24

With R1= Me and Et,

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62 0 rganop hosphorus Chemktry

r e a c t i o n a t 120° g i v e s a n e a r l y q u a n t i t a t i v e y i e l d of t h e phos- p h o r a m i d a t e ( 6 6 ) and t h e i m i d a z o l i n e ( 6 7 ) . 25

0: ‘\PO C(Ph 1 =CCI

0’

( 5 8 )

\

Me3SiN3 I

(60 1

/ r 1

I N3 Ph

(62 1

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 63

P-NR, 0’

+

N , R ~

( 6 4 )

2 R = CH,CH,NHCOCF,

R1 = Me I Et / - ‘ O”N/)>O I I I, NR2

R

( 6 6 1 ( 6 7 )

6 Five - and Six-membered-ring Phosphoranes. - I n a c o n x i n u a t i o n of ea r l ie r s t u d i e s a 6 , t h e f o r m a t i o n of phosphoranes (e.g. 71 ) from

p h o s p h i n i t e s (e .g . 68) and 2 -me thy l - l -n i t rop ropene ( 6 9 ) via ( 7 0 ) 27 h a s been shown t o be r e v e r s i b l e . E x p l o i t a t i o n of a n o t h e r

p o p u l a r r o u t e t o phosphoranes shows t h a t ( 7 2 ) reacts w i t h hexa-

f l u o r o a c e t o n e t o g i v e A5-dioxaphospholanes ( 7 3 ) and w i t h X = C 1 ,

h y d r o l y s i s g i v e s a c h i r a l phosphonic ester ( 7 4 ) 28

+ OMe Ph2POMe

P h,POMe I,O + 0- ( 6 8 ) I - __3 P h P ‘v’

CMe,-CHNO, - \C.CH + Me’ ‘Me

Me2C =CH NO, ( 7 0 )

( 6 9 ) (71) S3’P, -20

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64 Organophosphorus Chemktry

8 u P( X )NEt

( 7 2 )

0 I I

I N R

6 u P- 0 C ( CF3 12- C ( CF3 OH

(74)

Y x CI

X

(73) X = CI, F, or OCH(CF3 ),

T r i a l k y l p h o s p h i t e s ( 7 5 ) r e a c t w i t h p o l y f l u o r o a l i p h a t i c a ldehydes ( 7 6 ) t o form phosphoranes ( 7 7 ) c o n t a i n i n g t h e 1 , 4 , 2 -

dioxaphospholane r i n g , a n d t h e s t a b i l i t i e s of t h e s e phosphoranes

i n c r e a s e w i t h t h e number of p o l y f l u o r o a l k y l g roups i n each molecu le . 29

( 7 5 ) ( 7 6 ) R2 (77)

2 R' = Me or R = CF3, HCF2CF2 ,

HCFz CF, CH, HCF, (CF, 1 3 , or

C I C F2 ( CF2 l3

The r e a c t i o n s of t r i c o - o r d i n a t e d phosphorus compounds w i t h

1 , 2 - d i o n e s and o r t h o q u i n o n e s c o n t i n u e s t o a t t r a c t a t t e n t i o n a s e x e m p l i f i e d by t h e r e a c t i o n of hexamethylphosphorus t r i a m i d e ( 7 8 ) w i t h a s e r i e s of b e n z i l s ( 7 9 ) t o form phosphoranes (80) whose

s t r u c t u r e s were conf i rmed by n e g a t i v e 31P n . m . r . s h i f t s and phosphorus c o u p l i n g t o t h e ip so -ca rbons i n t h e 1 3 C n . m . r . s p e c t r a . I n t h e c a s e of t h e p , p ' - d i n i t r o adduct however, t h e 31P n . m . r . s h i f t was p o s i t i v e and t h e c o u p l i n g t o t h e ip so -ca rbons had d i s a p p e a r e d i n d i c a t i n g r a p i d i o n i z a t i o n . On c o o l i n g t h e c o u p l i n g w a s a l s o l o s t i n t h e p c h l o r o - and p , p ' - d i f l u o r o a d d u c t s .

30 -

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 65

The reaction of PC13 with a series of ortho-quinones (81) leads to the 2-phenylenedioxophosphoranes (83) and e.s.r. evidence is presented to substantiate the claim that the reaction proceeds through radical ion pairs (82) . (85) have also been postulated as intermediates in the reaction of

Monocyclic phosphoranes 31

(78 1 (79 )

X,Y =p-OMe

x , Y = p - M e

X , Y = p - F

X ,Y=p-NO,

X = H , Y = P - C I

(80)

trialkyl phosphites with the thiophene-2,3-dione (84) which ultimately gives (87) probably via (86) .

g-Aminophenyliminophosphoranes (88) feature in another equilibrating system giving rise t o A5-benzodiazaphospholes ( 89)33. data were obtained by n.m.r., depended markedly on the substituents and on the solvent used.

32

The position of the equilibrium, for which quantitative

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66 Organophosphorus Chemistry

R = Me, Et,Pr’ (84)

0 0 % \

(85 1 (86)

NHR’

D

R5 d

(88 ) ( 8 9 )

A s a s e q u e l t o t h e work on a c y c l i c p h o s p h ~ r a n e s ’ ~ , J a n z e n

e t a l . h a v e shown t h a t t h e h y d r o l y s i s of t h e m o n o c y c l i c p h o s p h o r - a n e s ( 9 0 ) - ( 9 2 ) u n d e r n e u t r a l , b a s i c , o r a c i d i c c o n d i t i o n s c a u s e s r i n g o p e n i n g t o g i v e (931 , (94) , and ( 9 5 ) r e s p e c t i v e l y . 34

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 67

CI

(90) (93)

OR

H20 or B

0 . I M - NaOH

0 II

I Ph- P- 0 C(CF3 1, C(CF3),0H

OH

(91 1 R = CH(CF3),, Ph, or Me (94 1

( 9 2 ) R = Et, Bun, or

Phosphoranes ( 9 6 )

H2S04 , 2 5 OC * (HO)2POC(CF3)2C(CF3)20H

Ph ( 9 5 1

p r e p a r e d by c h l o r i n a t i o n of t h e c o r r e s p o n d i n g p h o s p h i t e s are t h e r m a l l y s t a b l e and may i n many cases ( R = Me, But , or CC13 and X = C l ) be vacuum d i s t i l l e d above 100°C.

however ( and w i t h X = H o r C l ) t h e phosphoranes decompose by a t t a c k o f c h l o r i d e i o n on t h e a-or B-carbons of t h e d o u b l e bond t o g i v e ( 9 7 ) and ( 9 8 ) o r ( 9 9 ) and (100) r e s p e c t i ~ e l y ~ ~ .

When R 9 Ph

.

B i c y c l i c phosphoranes (102) have been p r e p a r e d i n t o l e r a b l e

y i e l d s (30-40%) by t h e r e a c t i o n of dialkylphosphoroisocyanatidites (101) w i t h ~ a l i c y l a l d e h y d e ~ ~ . A s t u d y o f t h e r e a c t i o n o f d i e t h y l p e r o x i d e w i t h b i c y c l i c p h o s p h o r a m i d i t e s (103) and ( 1 0 4 ) h a s been used t o p r o v i d e f u r t h e r e v i d e n c e f o r t h e b i p h i l i c i n s e r t i o n mechanism37. comple t e (89% y i e l d of 105) a f t e r s even d a y s whereas 89% r e a c t i o n t o ( 1 0 6 j r e q u i r e d t h i r t y days a t room t e m p e r a t u r e . Conver se ly

The f o r m a t i o n of ( 1 0 5 ) at Oo i n d i c h l o r o m e t h a n e w a s

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68 0 rganop hospho rus Chemistry

r e a c t i o n of ( 1 0 4 ) w i t h d i p h e n y l d i s u l p h i d e gave ( 1 0 7 ) w i t h i n

(RO 1 ,PNCO

(101 1

R = Et or

CLCH ,CH,

s e c o n d s a t room

\

( 9 9 )

+ cJ(,",",

+ PhCCL=CX,

x + PhCCX,CL

(100 1

I-

(102) b3'P, -40

t e m p e r a t u r e , p re sumab ly t h e c o n v e n t i o n a l n u c l e o p h i l i c d i s p l a c e m e n t mechanism, w h e r e a s (103) t o o k 10h unde r r e f l u x i n T H F t o g i v e a m i x t u r e of t h r e e compounds, t h e ma jo r component o f which w a s (108). I n c i d e n t a l l y (108) a p p e a r s t o b e t h e o n l y example of an i s o l a b l e phosphorane c o n t a i n i n g t w o a c y c l i c P-S bonds . The p a p e r a lso d e s c r i b e s t h e r e a c t i o n s of (103) and ( 1 0 4 ) w i t h b e n z e n e s u l p h e n a t e s t o g i v e t h e d i a l k o x y p h o s p h o r a n e s (109) and (110).

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 69

(105)

N-P

PhSSPh I (109) P?

R = CHzCF3

or CH { CF3 l2

I ,,SPh

/ I \SPh N-P'

Lo (108

/

*3 I 0 i-J

(104)

I PhSSPh

PhS

PhS

(107)

(110)

R = CH,CF,

or CH (CF3),

The t h e r m o l y s i s of t h e 7-phosphanorbornene (111) i n t h e p r e s e n c e of d i e n e s ( e A . 1 1 2 ) g i v e s t h e f r a g m e n t a t i o n p r o d u c t s ( 1 1 4 ) and (115) and a pentaalkylspirophosphorane (113) is p r o p o s e d as t h e c r i t i c a l i n t e r m e d i a t e i n t h i s r e a c t i o n . 38

C y c l i c s i l y l p h o s p h i t e s ( 1 1 6 a , b ) react w i t h b e n z i l t o f o r m

p h o s p h o r a n e s ( 1 1 7 ) a n d ( 1 1 8 ) w h i c h , on h e a t i n g , decompose t o a m i x t u r e of c y c l o p h o s p h a t e s ( 1 1 9 ) and ( 1 2 0 ) . 39

I n a c o n t i n u a t i o n o f s t u d i e s on h a l o g e n o p h o s p h o r a n e s , G loede h a s shown t h a t t h e s p i r o p h o s p h o r a n e ( 1 2 1 ) reacts w i t h t r i a r y l

p h o s p h i t e s t o g i v e ( 1 2 2 ) and ( 1 2 3 ) and w i t h a l k y l p h o s p h i t e s t o g i v e a m i x t u r e of ( 1 2 4 ) and ( 1 2 5 ) . The r e a c t i o n s of ( 1 2 1 ) w i t h p h o s p h o n a t e s , p h o s p h a t e s , and p e n t a o x y p h o s p h o r a n e s are r e p o r t e d i n t h e same p a p e r . N u c l e o p h i l i c d i s p l a c e m e n t of phenoxy g r o u p s f rom s p i r o p h o s p h o r a n e s ( 1 2 6 ) by a v a r i e t y of a l c o h o l s ( a p h o s p h o r a n y l -

4 0

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70 Organophosphorus Chemistry

R /O\POSiMe3 + 'Iph T

L O ' 0 Ph

(11 6 a,b) I I

(117) R = CH3CHCHCH3

(118) R = a

RT O'P ( 0 1 0 C P h 1 = C ( P h 0 S i M e3 P(0)OROSiMe3 L O '

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 71

a t i o n r e a c t i o n ) o c c u r s b y a t t a c k a t p h o s p h o r u s r a t h e r t h a n t h e

c a r b o n y l g r o u p t o g i v e s p i r o p h o s p h o r a n e s ( 1 2 7 ) . 41

OR a0\k/'n + CIP(OR),

0' '0

(122 1 (123 )

CL ao\k/'n + P(OR), 0' '0

(121 1

(124) (1 2 5 )

I .9 1 0 2 + PhOH

0 9

+ R ~ O H - O 7 PhO-PM'.

!TR1 0 Ro-v-R1 0

(126) R = Me or Ph ( 1 2 7 )

The r e a c t i o n of a c y c l i c p h o s p h o n i t e ( 1 2 8 ) w i t h c y c l i c d i s u l p h i d e s ( 1 2 9 a , b ) t o f o r m ( 1 3 0 a , b ) h a s been shown t o b e r e v e r - s i b l e w i t h t h e p o s i t i o n of e q u i l i b r i u m d e p e n d e n t upon t h e s o l v e n t , On t r e a t m e n t w i t h e t h y l e n e g l y c o l t h e phosphorane 42

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72 Organophosphorus Chemistry

(130a ) g a v e h i g h y i e l d s of ( 1 3 1 ) and ( 1 3 2 ) .

(128)

(130a) +

(1 29a, b)

a; Ar = & (130a, b )

b; Ar =

SH SH

HO

(133) R = H or Me

(134) R = H or Me

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 t h i o c a t e c h o l s (133)

and t h e i r t r i m e t h y l s i l y l a t e d d e r i v a t i v e s ( 1 3 4 ) p roduced o n l y

c h l o r o d i t h i o p h o s p h i t e s ( 1 3 5 ) and a t t e m p t s t o p r e p a r e p e r f l u o r o - p h e n y l t h i o phosphoranes (137) from phosphorus p e n t a c h l o r i d e and

(136) r e s u l t e d o n l y i n t h e f o r m a t i o n o f p e r f l u o r o p h e n y l t h i o phos-

p h i t e ( 1 3 8 ) and d i s u l p h i d e ( 1 3 9 ) . The r e a c t i o n of c y c l i c t h i o -

p h o s p h i t e s ( e d . 1 4 0 and 1 4 1 ) w i t h t h e d i t h i e t e n ( 1 4 2 ) however , l e d

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 73

a >PS Bun

Me

(s)pSB"n

S +

(139)

t o t h e s u c c e s s f u l p r e p a r a t i o n of two s p i r o p h o s p h o r a n e s ( 1 4 3 and 43 1 4 4 ) each c o n t a i n i n g f i v e phosphorus-sulphur bonds .

A n i l i n e h y d r o c h l o r i d e c a t a l y s e s t h e c o n v e r s i o n of t h i a z a p h o s -

pho lane ( 1 4 5 ) i n t o t h e sp i rophosphorane (146) c o n t a i n i n g P-N and P-S bonds . The same pape r r e p o r t s t h a t t h e r e a c t i o n of t h e c y c l i c p h o s p h o n i t e (147) w i t h d i a l k y l a m i n e s l e a d s e v e n t u a l l y t o t h e

sp i rophosphorane (148) t h e r o u t e shown whereas p r imary amines ( e 2 . b e n z y l m i n e ) w i t h ( 1 4 7 ) g i v e s t h e monocycl ic phosphorane (149) c o n t a i n i n g a P-H bond.

b y (151) [formed b y

44

Sp i rophosphoranes c o n t a i n i n g f i v e P-N bonds are r e p r e s e n t e d s i m p l e amine s u b s t i t u t i o n on (150)j and t h e

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74 Organophosphorus Chemistry

( 1 4 5 ) ( 1 4 6 )

Et

+ EtP(NR,), 2 OPEt NR,

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 75

c r y s t a l s t r u c t u r e of (151) r e v e a l s a n e a r l y t r i g o n a l - b i p y r a m i d a l phosphorus atom t o g e t h e r w i t h a t e t r a h e d r a l phosphorus atom at t h e phosphory l group . 45

Ph Ph

Me-N N 0 /

CL -P

\

Me-N N 0 \ / \ / NH3 ~ H N- \/ \pH

* / \ N / \ p h Me-N Me-N

N4Ph Ph

Compounds ( 1 5 2 ) and (153) have been s y n t h e s i z e d as models f o r CAW, and v a r i a b l e t e m p e r a t u r e I3C n .m. r . s t u d i e s r e v e a l t h a t t h e d ioxaphosphor inane r i n g i n (152) p r e f e r s t h e a p i c a l - e q u a t o r i a l a l ignmen t ( A G * = 42 kJ rnol-l , xc = -64OC) whereas l i g a n d exchange i n (153) is f a s t on t h e n.m. r . t i m e scale even a t -72OC. d i f f e r e n c e is a s c r i b e d t o b o t h e l e c t r o n i c and s t e r i c ( s t r a i n ) e f f e c t s imposed by t h e a n n e l a t e d f u r a n r i n g R e a c t i o n of t h e oxad iazaphospho lane (154) w i t h Ph3P/CC14 gave a compound a s c r i b e d s t r u c t u r e (155) which on t r e a t m e n t w i t h water gave t h e

47 d ioxad iazaphosphor inane (156) .

The

OMe

MeO., I OMe

MeO.., I

Meo'Qo (153)

(152)

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76

H

0 rganop hospho rus Chem ktry

N j N \

Ph 3PC12/Et$J

phA0’pph3\ ( 1 5 4 ) r

I I ‘PPh, CL- L

+ CL- PPh,

I

HN

(156) 1

PPh3 (155)

7 Hexaco-o rd ina ted Phosphorus Compounds. - R e p o r t s i n t h i s area d u r i n g t h e y e a r h a v e been s p a r s e . A p r o t o n n . m . r . s t u d y of c r y s t a l l i n e NH4PF6 r e v e a l s t h a t t h e ammonium i o n is e x e c u t i n g f a s t mo t ion e v e n a t 1 4 k b a r and 77K and h e n c e t h e p o t e n t i a l b a r r i e r f o r mot ion of t h e ammonium i o n ( s u r r o u n d e d by s i x , s y m m e t r i c a l l y d i s - p o s e d , PF; i o n s ) is l o w , even u n d e r p r e s s u r e .

of t h e 19F n . m . r . s p e c t r u m a t 77K i n c r e a s e d w i t h p r e s s u r e which was a s c r i b e d t o an i n c r e a s e d d i s t o r t i o n of t h e o c t a h e d r a a t h i g h p r e s s u r e .

F i n a l l y , 31P n .m. r . s p e c t r o s c o p y l e d t o i d e n t i f i c a t i o n , s o l u t i o n , o f s e v e r a l u n s t a b l e i o n s i n t h e ser ies [PC16-n(NCO) I - and [PC16-n(OCN)n 1 -. method o f pairwise i n t e r a c t i o n s f rom t h e o b s e r v e d c h e m i c a l s h i f t s

The s l i g h t asymmetry

48

Isomeric c o n f i g u r a t i o n s were a s s i g n e d by t h e 49 .

1 2 3 4 5 6

7 8

9

10

11

12

RE f e r e n ces

J . B . Husband and A. M c N a b , Phosphorus S u l f u r , 1984, 20 ( 2 1 , 207. J. Navech and J . -P . Majoral, Phosphorus S u l f u r , 1983, 15 (11, 51. D. G. G o r e n s t e i n , P r o g r . Nucl . Magn. Reson. S p e c t r o s c . , 1983, 16, p.1. Phosphorus S u l f u r , 1983, 18 (1-3) pgs. 81, 8 5 , 8 9 , 9 7 , 455 , 457, and 460. C . J . Marsden, J. Chem. SOC. , Chem. Commun. , 1984, ( 7 ) , 401. R . A . J . J a n s s e n , G . J . V i s s e r , and H.M. Buck, J.Am. Chern. Soc . , 1984, 106, 3429. M. U1-Haque , J.Ahmed , and W . Horne, A c t a C r y s t a l l o q r . , 1983, C39, 1048. A. Dubourq , R. Roques , J. P. Declercq, D. Boyer , L. Lamande , A.Munoz, and R.Wolf, Phosphorus S u l f u r , 1983, 17 (11, 97. D.H.R. Barton , B . C h a r p i o t , E.T.Huu Dau, W.B. M o t h e r w e l l , C. P a s c a r d , and C. P i c h o n , Helv. Chirn. A c t a , 1984, 67, 586. J . J . C . v a n L i e r , R.J .M. H e r m a n s , and H . M . Buck, Phosphorus S u l f u r , 1984, 1 9 (11, 173. G.-V. R h c h e n t h a l e r , R . Bohlen , W. S t o r z e r , A.B. S o p c h i k , and - W.G. B e n t r u d e , Z. Anorq. A l l g . Chem., 1983, 507, 93. S . J . Brown and J . H . C l a r k , J . Chem. S O C . , Chem. Commun., 1983, 1256.

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2: Pentaco-ordinated and Hexaco-ordinated Compounds 77

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L . I . Kudryavtseva,N.G. Feshchenko, and M . I . Povolo tsk i i , J. Gen. Chem. USSR (Engl. Transl . ) , 1983, 53 ( 1 2 , p t . 1) , 2420. D.B. Denney, D.Z. Denney, and L i u Lun-Tsu, Acta. Chim. S i n i c a , 1984, 42 ( 3 ' , 293. P.D. Beer, R.C. Edwards, C.D. H a l l , J . R . Jennings, and R . J . Cozens, Phosphorus S u l f u r , 1983, 17 (31, 283. W.C. Archie ,Jr . and F.H. Westheimer, J .Am. Chem.Soc., 1973, 95, 5955. A. Queen, A.E. Lemire, and A.F. Janzen, I n t . J . Chem. K i n e t . , 1981, 13, 411. A.B. R e i t z , M.S. Mutter , and B.E. Maryanoff,J.Am.Chem. SOC., 1984, 106, 1873. F. E l Khat ib , A . 14. Caminade, and M. Koenig, Phosphorus Sul fur , 1984, 20, cc 2 J .

E. L . Clennan and P. Choo Heah, J. Org. Chem., 1983, 48, 2621. V. I. Kal'chenko, V.V. Neqrebetski i , R.B. Rudyi, L . I . A t a m a s , M . I . Pavo- l o t s k i i , and L.N. Markovskii, J. Gen. Chem. USSR (Engl. Transl . ) ,1983, - 53 (4 , pt.21, 821. ~

Yu. G. Shermolovich, A.V. Solov 'ev, E.A. Danchenko, and L.M. Markovskii, J. Gen. Chem. USSR (Engl. T r a n s l . ) , 1983, 2 ( 9 , pt .2) , 1940. T.V. Kolodka and Yu. G. Gololcbov, J.Gen. Chem. USSR (Engl. Transl . ) , 1983, - 53 (5 ,p t . 11, 895. Yu. Budilova, N . I . Gusar, and Yu. G. Gololobov, J . Gen. Chem. USSR (Engl. Transl . 1, 1983, 53 (2, p t . 11, 247. N . I . Gusar, M.P. Chaus, and Yu. G. Gololobov, J. Gen. Chem. USSR (Engl. Transl . ) , 1983, 53 (11, p t . 11, 2237. R.D. Gareev, I . M . Shermergorn, and A.N. Pudovik, J. Gen. Chem. USSR (w. Transl . ) , 1981, 51 (9 , p t . 21, 1838. R.D. Gareev, A.N. Pudovik, and I . M . Shermergorn, J. Gen. Chem. USSR (w. Transl . ) , 1983, 53 (1, p t . I), 27. R. Francke, G.-V. Raschenthaler , R. D i Giacomo, and D . Daktenieks, Phosphorus S u l f u r , 1984, 20, 107. L. N. Markovskii , N.P. Kolesnik , Yu. L. Bakhmutov , A.A. Kudryavtsw , and Yu. G. Shermolovich, J. Gen. Chem. USSR (Engl. Transl . ) , 1983, 53 (9 , p t . 11, 1799. D.B. Denney and S.D. P a s t o r , Phosphorus S u l f u r , 1983, 16, 239. E.S. Klimov, A.A. Bumber , and 0. Y u . Okhlobystin, J. Gen. Chem. USSR (Engl. Trans l . ) ,1983, 53 (8 , p t . 11,1565.

M.M. Sidky, W.M. Abdou, and N.M. Abd-El-Rahman, Phosphorus S u l f u r , 1983, 16, 331. H.B. Stegmann, G. Wax, S. Pe ine l t , and K. S c h e f f l e r , Phosphorus S u l f u r , 1983, 16, 277. A . F . Janzen, A.B. Lemire, R.K. Marat, and A . Queen, Can. J. Chem. , 1983, 61, 2264. T.V. Kolodka, R.A. Loktionova, and Yu. G. Gololobov, J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1983, 53 (11,pt . 11, 2233.

R . I . Tarasova, N . I . S i n i t s y n a , T.A. Droinishnikova, and V.V. Moskva, J. Gen. Chem. USSR (Engl. Transl . ) , 1983, 53 (3 ,pt . 21, 605. D.B. Denney, D.Z. Denney, P . J . Hammond, C . Huang, L.-Tsu Liu , and KrShu Tseng, Phosphorus S u l f u r , 1983, 2, 281. K.C. Cas te r and L.D. Quin , Tetrahedron L e t t . , 1983, 2 4 (521, 5831. V.V. Ovchinnikov, Yu. G. Eus ta f ' eva , R.A. Cherkasov, and A.N. Pudovik, J. Gen. Chem. USSR (Engl. Transl.), 1983, 53 (8 , p t . 21, 1732. J. Gloede, Phosphorus s u l f u r , 1984, 20, 15. S. Kobayashi, Y . Murukawa, T. Hashimoto, and T. Saegusa, Chem. L e t t . , 1980, 1599. Y. Kimura, T. Kokura, and T. Saegusa, J. Org. Chem., 1983, 48 (211, 3815. D.B. Denney, D.Z. Denney, and Liu Lun-Tsu, Acta Chim. S i n i c a , 1984, 42 (41, 340.

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M.A. Pudovik, Yu. B. Mikhailov, and A.N. Pudovik, J. Gen. Chem. USSR (Engl. Transl . ), 1983, 53 (9, p t . 1). 1759.

R.O. Day, A.Schmidpeter, and R.R. Holmes, Inorg. Chem., 1983, 22, 3696.

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78 Organophosphorus Chemistry

46 P.J.J. M.van 001 and H . M . Buck, R e c u e i l , J . Roy. Nether . Chem. SOC., 1984,

47 I.N. Zhmurova, V.G. Yurchenko, and A.M. Pinchuk, J. Gen. Chem. USSR

48 R. Kaliaperumal, R. S r in ivasan ,and K.V. Ramanathan, Chem. Phys. L e t t . ,

49 K. B. D i l l o n and A.W.G. P l a t t , Phosphorus S u l f u r , 1984, 19, 299.

103, 119.

(EngLTransl . ) , 1983, 53 ( 7 , pt.11, 1361.

1983, 102 (l), 29.

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