This work has been digitalized and published in 2013 by Verlag Zeitschrift für Naturforschung in cooperation with the Max Planck Society for the Advancement of Science under a Creative Commons Attribution4.0 International License.

Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschungin Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung derWissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht:Creative Commons Namensnennung 4.0 Lizenz.

Cyclopentyl- und Cyclohexyl-dimethyl-methylen-phosphoran aus co-Haloalkyl-trimethylphosphonium-salzen. Goldkomplexe mono- und difunktioneller Ylide

C y c l o p e n t y l - a n d C y c l o h e x y l - d i m e t h y l - m e t h y l e n e - p h o s p h o r a n e s

f r o m c o - H a l o a l k y l - t r i m e t h y l p h o s p h o n i u m S a l t s .

G o l d C o m p l e x e s o f M o n o - a n d D i f u n c t i o n a l Y l i d e s

H . S c h m i d b a u r * u n d H . P . S c h e r m

A n o r g a n i s c h - c h e m i s c h e s I n s t i t u t d e r T e c h n i s c h e n U n i v e r s i t ä t M ü n c h e n , L i c h t e n b e r g s t r a ß e 4 , D - 8 0 4 6 G a r c h i n g

Z . N a t u r f o r s c h . 8 4 b , 1 3 4 7 - 1 3 5 1 ( 1 9 7 9 ) ; e i n g e g a n g e n a m 2 5 . J u n i 1 9 7 9

P h o s p h o r a n e s , Y l i d e s , G o l d C o m p l e x e s

( C H 3 ) 3 P c o n v e r t s a , a > - d i b r o m o p e n t a n e a n d - h e x a n e i n t o c o - b r o m o a l k y l t r i m e t h y l p h o s -p h o n i u m b r o m i d e s , w h i c h u n d e r g o a c y c l i z a t i o n o n t r e a t m e n t w i t h N a N H 2 i n t e t r a h y d r o -f u r a n e t o f o r m t h e c y c l o p e n t y l - a n d c y c l o h e x y l - d i m e t h y l - m e t h y l e n e p h o s p h o r a n e s 4 a n d 5 . F r o m t h e b i s - p h o s p h o n i u m s a l t ( C H 3 ) 3 P ( C H 2 ) 6 P ( C H 3 ) 3 2 © 2 B r © t h e d i f u n c t i o n a l b i s - y l i d e C H 2 = ( C H 3 ) 2 P ( C H 2 ) 6 P ( C H 3 ) 2 = C H 2 ( 7 ) i s o b t a i n e d . T h e y l i d e 4 w a s c h a r a c t e r i z e d b y t h e c r y s t a l l i n e m e t a l l o c y c l i c A u ( I ) d e r i v a t i v e 8 . 7 f o r m s a p o l y m e r i c g o l d c o m p l e x .

3 - H a l o p r o p y l - t r i m e t h y l p h o s p h o n i u m s a l z e w e r d e n

b e i d e r E i n w i r k u n g s t a r k e r B a s e n i n C y c l o p r o p y l -

d i m e t h y l - m e t h y l e n - p h o s p h o r a n v e r w a n d e l t [1] . I m

G e g e n s a t z d a z u e n t s t e h t a u s 4 - H a l o b u t y l - t r i m e t h y l -

p h o s p h o n i u m s a l z e n be i g l e i c h e r R e a k t i o n s f ü h r u n g

1 - M e t h y l - 1 - m e t h y l e n - l ^ . 5 -phosphorinan [2], I m

e r s t e r e n F a l l w i r d d i e a l t e r n a t i v d e n k b a r e P h o s -

p h e t a n b i l d u n g e b e n s o u n t e r d r ü c k t w i e i m z w e i t e n

F a l l d e r C y c l o b u t a n r i n g s c h l u ß , d a d i e j e w e i l i g e n

K o n k u r r e n z r e a k t i o n e n o f f e n b a r w e s e n t l i c h s c h n e l -

ler s ind. A u f d e r S u c h e n a c h Y l i d e n , d e r e n P h o s p h o r -

a t o m in d e n s i e b e n g l i e d r i g e n P h o s p h e p a n r i n g o d e r

i n e in A c h t r i n g s y s t e m e i n g e b a u t i s t , h a b e n w i r j e t z t

die R e a k t i o n v o n 5 - H a l o p e n t y l - u n d 6 - H a l o h e x y l -

p h o s p h o n i u m s a l z e n s t u d i e r t , b e i b e i d e n B e i s p i e l e n

a b e r n u r C y c l o a l k y l i e r u n g b e o b a c h t e t .

Ergebnisse

5-Brompentyl- und 6-bromhexyl-phosphonium-bromid 1 . 5 - D i b r o m p e n t a n s e t z t s i c h i n B e n z o l be i 2 5 °C

i m L a u f e e i n i g e r W o c h e n m i t s t ö c h i o m e t r i s c h e n

M e n g e n (CH3)3P z u r g e s u c h t e n S a l z v o r s t u f e 1 u m ,

o h n e d a ß i n n e n n e n s w e r t e r M e n g e N e b e n p r o d u k t e

e n t s t e h e n . M i t 1 . 6 - D i b r o m h e x a n k o m m t es d a g e g e n

u n t e r a n a l o g e n B e d i n g u n g e n i m m e r a u c h z u r B i l -

d u n g d e s D i p h o s p h o n i u m s a l z e s 3, d a s d u r c h B e -

* S o n d e r d r u c k a n f o r d e r u n g e n a n P r o f . D r . H . S c h m i d -b a u r .

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h a n d l u n g m i t E t h a n o l v o m e r w a r t e t e n M o n o -

q u a t e r n i e r u n g s p r o d u k t 2 a b g e t r e n n t w e r d e n k a n n .

© © Br(CHj)5 Br • (CH3]3P • [ICH3)3 P(CH2)5Br] Br 1

© O Br(CH2)6Br • ICH3)3 P ^ [ ICH j l j P(CH2) sBr] Br 2

tCH3)3PV- »- [ ICHj l j PICH2)6PICH3)3 I 2Br® 3

D i e d r e i P h o s p h o n i u m s a l z e s i n d f a r b l o s e , te i l -

w e i s e h y g r o s k o p i s c h e (2) F e s t s t o f f e , d i e i n W a s s e r

u n d C F 3 C O O H g u t lös l i ch s i n d . I h r e u n d 3 1 P - N M R - S p e k t r e n s i n d i m E x p e r i m e n t a l t e i l z u -

s a m m e n g e s t e l l t . 1 u n d 2 z e i g e n i n d e n i H - S p e k t r e n

k l a r g e t r e n n t v o n d e n ü b r i g e n R e s o n a n z e n d a s

T r i p l e t t d e r c o C K b B r - G r u p p e . I n d e n I R - S p e k t r e n

f i n d e t s ich d e m e n t s p r e c h e n d j e w e i l s e ine s t a r k e

v ( C B r ) - S c h w i n g u n g f ü r d ieses S t r u k t u r e l e m e n t . F ü r

3 w i r d k e i n e s d ieser b e i d e n C h a r a k t e r i s t i k a m e h r

g e f u n d e n .

Cyclopentyl- und Cyclohexyl-dimethyl-methylen-phosphoran

B e i d e r E i n w i r k u n g v o n N a N I h a u f 1 u n d 2 i n

s i e d e n d e m T e t r a h y d r o f u r a n [3] t r i t t e i n e s t ü r m i s c h e

N H 3 - E n t w i c k l u n g e in . A u s d e r R e a k t i o n s m i s c h u n g

k ö n n e n a n s c h l i e ß e n d d u r c h D e s t i l l a t i o n f a r b l o s e ,

h o c h r e a k t i v e f lüss ige P r o d u k t e i s o l i e r t w e r d e n . D i e

A u s b e u t e n b e t r a g e n 5 5 - 6 5 % :

D i e a n a l y t i s c h e n D a t e n e r l a u b e n z u n ä c h s t k e i n e

E n t s c h e i d u n g ü b e r d ie S t r u k t u r a l t e r n a t i v e n d e r

I s o m e r e n 4/4 a b z w . 5/5 a. (Es sei b e t o n t , d a ß 4 a u n d

5 a k e i n e r e i n f i k t i v e n A n n a h m e n d a r s t e l l e n , s o n d e r n

1348 H. Schmidbaur-H. P. Scherm • Cycloalkyl-dimethyl - methy len -phosphorane 1348

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P h o s p h o r i n a n s e c h s r i n g e r h a l t e n w i r d ! [2].) D i e

d e t a i l l i e r t e A u s w e r t u n g d e r 1 H - u n d 1 3 C - N M R -

S p e k t r e n z e i g t j e d o c h s o f o r t , d a ß a u s s c h l i e ß l i c h 4

u n d 5 v o r l i e g e n . D i e 1 H - g e k o p p e l t e n 1 3 C - S p e k t r e n

e r g a b e n spez ie l l f ü r C - l j e w e i l s d ie e r w a r t e t e

D u b l e t t a u f s p a l t u n g , d ie b e i 4 a / 5 a n i c h t a u f t r e t e n

k a n n . D i e R e s o n a n z d e s y l i d i s c h e n C - A t o m s , d ie

k l a r a b g e s e t z t bei h ö c h s t e n F e l d s t ä r k e n e r s c h e i n t ,

i s t d a g e g e n z u m T r i p l e t t a u f g e s p a l t e n , w o d u r c h

e n d o c y c l i s c h e Y l i d f u n k t i o n e n s icher a u s g e s c h l o s s e n

w e r d e n k ö n n e n . D i e N M R - D a t e n s ind z u m V e r -

g l e i c h i n T a b . I z u s a m m e n g e s t e l l t . D i e I R - S p e k t r e n

d e r Y l i d e s i n d d u r c h die v(P=C)- u n d <5(P=CH)-

S c h w i n g u n g e n g e k e n n z e i c h n e t , o h n e d a ß a b e r

d i r e k t e S c h l ü s s e a u f d ie S t r u k t u r g e z o g e n w e r d e n

k ö n n t e n .

Z u r D e r i v a t i s i e r u n g w u r d e 4 i n D i e t h y l e t h e r m i t

t r o c k e n e m H C l u m g e s e t z t , w o b e i q u a n t i t a t i v C y c l o -

p e n t y l - t r i m e t h y l p h o s p h o n i u m s a l z 6 g e b i l d e t w u r d e :

D i e s e s k o r r e s p o n d i e r e n d e S a l z k o n n t e w i e die V o r -

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

fiziert w e r d e n .

D i e U m s e t z u n g des D i q u a r t ä r s a l z e s 3 m i t N a N H 2

l i e f e r t d a s D o p p e l y l i d 7 , d a s b e i m E r k a l t e n in

s c h ö n e n f a r b l o s e n N a d e l n k r i s t a l l i s i e r t :

H,C CH, © © © NaNH, 2 \ / 3

I(CH3)3P(CH2)6P(CH3)3] 2Br > P CH2 CH, CH2 CH, nm3 / \ / \ / \ / \ /

-NaBr H,C CH, CH, CH, P •l 3 2 2 2 / \ ° CH3 CH2

D i e a n a l y t i s c h e u n d s p e k t r o s k o p i s c h e C h a r a k t e r i -

s i e r u n g b e r e i t e t k e i n e S c h w i e r i g k e i t e n . E i n z e l h e i t e n

g i b t d e r E x p e r i m e n t a l t e i l .

Gold(I)-komplexe des Monoylids 4 und des Doppelylids 7

P h o s p h o r y l i d e b i l d e n m i t G o l d ( I ) - V e r b i n d u n g e n

b e s o n d e r s s t a b i l e K o m p l e x e , d ie s i c h g u t z u r

C h a r a k t e r i s i e r u n g dieser Y l i d e e i g n e n [2, 4, 5]. A u s

d i e s e m G r u n d e w u r d e n a u c h 4 u n d 7 in A u ( I ) -

D e r i v a t e ü b e r g e f ü h r t . E r s t e r e s e r g i b t t a t s ä c h l i c h

T a b e l l e . N M R - S p e k t r e n d e r Y l i d e 4 u n d 5 a .

m

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< 5 ( C H 3 ) [ 2 J ( P H ) ] 1 , 1 6 [ 1 2 , 4 ] 1 , 0 1 [ 1 2 , 6 ] < 5 ( P C H 2 ) [2J ( P H ) ] — 0 , 6 0 [ 7 , 1 ] — 0 , 2 5 [ 7 , 1 ] •5(C5/6H»/H) 1 , 3 4 - 1 , 9 2 [ m ] 0 , 8 1 - 1 , 9 3 [ m ]

< 5 ( C H 3 ) \}J ( P C ) ] 1 5 , 0 0 [ 6 1 , 0 ] 1 3 , 8 6 [ 5 8 , 6 ] \}J ( C H ) ] q [ 1 2 8 , 2 ]

Ö ( P C H 2 ) [ i J ( P C ) ] — 1 1 , 2 7 [ 9 2 , 8 ] — 9 , 5 4 [ 8 7 , 9 ] [ V ( C H ) ] t [ 1 4 8 , 9 ]

ö(C-l) [ V ( P C ) ] 4 0 , 2 4 [ 5 1 , 3 ] 4 0 , 1 4 [ 5 1 , 3 ] [ V ( C H ) ] d [ 1 2 9 , 4 ]

ö(C-2) [ 2 J ( P C ) ] 2 7 , 0 3 [ 9 , 2 ] 2 6 , 9 2 k l e i n \}J ( C H ) ] t [ 1 2 8 ]

<5(C-3) [ i J ( C H ) ] 2 6 , 4 9 t 2 6 , 2 7 [ 1 2 8 ]

<5(C-4) \}J ( C H ) ] — — 2 5 , 6 3 [ 1 2 8 ]

d(P) { i H } 1 1 , 5 — 1 0 , 2 —

a ö - W e r t e i n p p m g e g e n T M S i n t , ( l H , 1 3 C ) b z w . H 3 P O 4 e x t . ( 3 1 P ) . B e n z o l - d 6 a l s L ö s u n g s m i t t e l b e i 3 0 ° C . D e n P r o b e n w u r d e z u r U n t e r d r ü c k u n g d e s P r o t o n e n a u s t a u s c h e s e t w a s L i A H U z u g e g e b e n . D a s 1 3 C - N M R - S p e k t r u m v o n 4 w u r d e , , o f f - r e s o n a n c e " g e m e s s e n u n d n u r d i e M u l t i p l i z i t ä t e n r e g i s t r i e r t , d a s d e s 5 i s t j e d o c h 1 H - g e -k o p p e l t a u f g e n o m m e n w o r d e n .

H. Schmidbaur-H. P. Scherm • Cycloalkyl-dimethyl - methy len -phosphorane 1349

e i n g u t k r i s t a l l i s i e r e n d e s l u f t s t a b i l e s P r o d u k t , f ü r

d a s b i s h e r i g e E r f a h r u n g e n e i n e A c h t r i n g s t r u k t u r

e r w a r t e n l a s s e n [2, 5] . D i e 1 H - N M R - S p e k t r e n e r -

g e b e n f ü r d i e C H 2 - P r o t o n e n b e i { 3 1 P } - E n t k o p p l u n g

n u r e i n A B - S p i n s y s t e m , d a s d i e Ä q u i v a l e n z d e r v i e r

C H 2 - G r u p p e n a n d e u t e t :

4 - 4 + 2 ( C H 3 ) 3 P A U C 1

2 ( C H 3 ) 3 P + 2 • 6 +

?"3

H CH^u-CHjOp J * 8

D a s M a s s e n s p e k t r u m b e s t ä t i g t d u r c h A u f t r e t e n d e s

M o l e k ü l i o n s b e i vi je = 680 d i e d i m e r e N a t u r d e s

K o m p l e x e s . D a s I R - S p e k t r u m z e i g t d i e v ( A u C ) -

S c h w i n g u n g e n b e i 5 5 2 c m - 1 .

M i t 7 w i r d u n t e r v e r g l e i c h b a r e n B e d i n g u n g e n n u r

e i n f a r b l o s e s u n l ö s l i c h e s M a t e r i a l e r h a l t e n , a u s d e m

d a s a l s N e b e n p r o d u k t g e b i l d e t e D i p h o s p h o n i u m s a l z

(3, C l s t a t t B r ) m i t M e t h a n o l h e r a u s g e l ö s t w e r d e n

k a n n . E s e r s c h e i n t p l a u s i b e l , d a ß e s s i c h u m e i n

P o l y m e r e s 9 h a n d e l t :

2 - 7 + 2 ( C H 3 ) 3 P A U C 1

2 ( C H 3 ) 3 P + 3 ( C l e ) +

(CHjlg ^Hj-AU-CHJ /CH3

/ p \ CH3 CH2-AU-CH2

D a s I R - S p e k t r u m w e i s t w i e d e r d i e ^ ( A u C ) - B a n d e

b e i 5 5 5 c m - 1 a u f . D a s i H - N M R - S p e k t r u m d e s P h o s -

p h o n i u m s a l z e s i s t m i t d e m d e s B r o m i d s 3 i d e n t i s c h .

D a s P o l y m e r e s e l b s t e r g i b t e i n e z u f r i e d e n s t e l l e n d e

E l e m e n t a r a n a l y s e . E s z e r s e t z t s i c h e r s t b e i 4 7 8 K ,

i s t a b e r l i c h t e m p f i n d l i c h .

Biskussion

D i e E r g e b n i s s e z e i g e n , d a ß v o n d e n c o - B r o m a l k y l -

t r i m e t h y l p h o s p h o n i u m s a l z e n

[ ( C H 3 ) 3 P « - ( C H 2 ) n - B r ] B r © m i t n = 3 - 6 l e d i g l i c h

j e n e s m i t n = 4 z u e i n e m P h o s p h a c y c l u s d e h y d r o -

h a l o g e n i e r t w i r d , n ä m l i c h z u m s p a n n u n g s f r e i e n

P h o s p h o r i n a n [1] , A l l e a n d e r e n d a g e g e n w e r d e n i n

C a r b o c y c l e n v e r w a n d e l t , w a s b e s t e h e n d e R e g e l n

ü b e r „ M i t t l e r e R i n g e " b e s t ä t i g t [6]. P h o s p h e t a n - ,

P h o s p h o l a n - , P h o s p h e p a n - u n d a n d e r e R i n g g r ö ß e n

m ü s s e n a l s o a u f a n d e r e n W e g e n a u f g e b a u t w e r d e n

( z . B . [ 1 , 2 ] ) .

W ä h r e n d d e r a u s 4 e r h ä l t l i c h d i m e r e G o l d k o m p l e x

8 s i c h s t r u k t u r e l l z w e i f e l l o s d e n r ö n t g e n o g r a p h i s c h

g e s i c h e r t e n H o m o l o g e n a n s c h l i e ß t [2, 5] , i s t d a s

p o l y m e r e D e r i v a t v o n 7 e i n e n e u e S t r u k t u r v a r i a n t e

(9). D a s S y s t e m w e i c h t o f f e n b a r d e r p r i n z i p i e l l g e -

g e b e n e n M ö g l i c h k e i t e i n e r k ö r b c h e n a r t i g e n S t r u k -

t u r , i n d e r d i e ( C H 2 ) 6 - K e t t e e i n e n „ H e n k e l " b i l d e t ,

a u s (9 a) .

9a

'CH3 H r f ' ^ C H z - A u - C ^ CH2-Au-CHf

V e r b i n d u n g e n d e s z w e i w e r t i g e n P l a t i n s h a t t e n

k ü r z l i c h d e r a r t i g e S t r u k t u r p h ä n o m e n e a u f g e z e i g t

[7], d o c h i s t f ü r s ie d i e h i e r g e w ä h l t e K e t t e n l ä n g e

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

Experimentelles (5-Brompentyl)-trimethylphosphonium-bromid (1)

2 , 7 7 g (36,4 m m o l ) T r i m e t h y l p h o s p h i n w e r d e n m i t 50 m l B e n z o l v e r d ü n n t u n d 8 ,47 g (36,8 m m o l ) 1 . 5 - D i b r o m p e n t a n z u g e s e t z t . N a c h 4 W o c h e n w i r d d a s g e b i l d e t e P h o s p h o n i u m s a l z a b f i l t r i e r t , m i t P e n -t a n g e w a s c h e n u n d a m V a k u u m g e t r o c k n e t . F a r b -l o s e s P u l v e r , d a s b e i 6 5 9 K (386 °C) s c h m i l z t ( D S C ) . A u s b e u t e : 1 0 , 7 g ( 9 5 % ) .

C 8 H i 9 B r 2 P (306,02)

B e r . C 3 1 , 4 0 H 6 , 2 6 , G e f . C 3 1 , 5 2 H 6 , 3 6 .

(6-Bromhexyl)trimethylphosphonium-bromid (2) und n-Hexyl-1.6-bis(trimethylphosphonium)-dibromid (3)

7 , 4 8 g (98 m m o l ) T r i m e t h y l p h o s p h i n u n d 2 4 g (98,4 m m o l ) 1 . 6 - D i b r o m h e x a n w e r d e n i n e i n e m a b -g e s c h m o l z e n e n B o m b e m o h r 1 4 d l a n g a u f 3 7 3 K e r h i t z t . D a s e n t s t a n d e n e S a l z w i r d i n E t h a n o l a u f -g e s c h l ä m m t u n d filtriert. D e r u n l ö s l i c h e R ü c k s t a n d (3) w i r d m i t P e n t a n g e w a s c h e n u n d a m V a k u u m g e t r o c k n e t . F a r b l o s e s , f e i n k r i s t a l l i n e s S a l z . S c h m p . : 603 K (330 °C). A u s b e u t e : 9 , 6 5 g ( 4 0 % ) .

C i 2 H 3 0 B r 2 P 2 ( 3 9 6 , 1 3 )

B e r . C 3 6 , 3 8 H 7 , 6 3 , G e f . C 3 6 , 1 2 H 7 , 5 1 .

D i e a b g e t r e n n t e e t h a n o l i s c h e L ö s u n g w i r d e i n -g e e n g t , b i s e i n Ö l - S a l z g e m i s c h z u r ü c k b l e i b t . D i e s e s w i r d m e h r m a l s m i t P e n t a n d i g e r i e r t , w o b e i d i e ü b e r s t e h e n d e L ö s u n g v e r w o r f e n w i r d . D e r e r h a l t e n e z ä h e S a l z b r e i (2) w i r d b e i I O - 4 b a r l ä n g e r e Z e i t g e t r o c k n e t , u m d a s a n h a f t e n d e S o l v e n s z u e n t -f e r n e n . F a r b l o s e s , s e h r h y g r o s k o p i s c h e s S a l z . S c h m p . : 4 6 3 K ( 1 9 0 °C). A u s b e u t e : 9 , 0 g ( 2 8 % ) .

C 9 H 2 i B r 2 P (320,05)

B e r . C 3 3 , 7 7 H 6 , 6 1 , G e f . C 3 4 , 3 1 H 6 , 8 7 .

1350 H. Schmidbaur-H. P. Scherm • Cycloalkyl-dimethyl - methy len -phosphorane 1350

Cyclopentylf dimethyl)methylenphosphoran (4) 9 , 5 g ( 3 1 , 0 m m o l ) 1 u n d 3 ,6 g (92,5 m m o l )

N a t r i u m a m i d w e r d e n i n 100 m l T H F u n t e r R ü h r e n z u m S i e d e n e r h i t z t .

N a c h b e e n d e t e r A m m o n i a k e n t w i c k l u n g f i l t r i e r t m a n d a s e n t s t a n d e n e N a t r i u m b r o m i d a b u n d w ä s c h t m i t T H F n a c h . A u s d e m F i l t r a t w i r d d a s S o l v e n s b e i N o r m a l d r u c k a b d e s t i l l i e r t u n d d e r R ü c k s t a n d b e i r e d u z i e r t e m D r u c k f r a k t i o n i e r t . B e i 3 4 2 K / 3 - I O " 3 b a r (69 ° C / l T o r r ) d e s t i l l i e r t 4 a l s f a r b -l o s e F l ü s s i g k e i t ü b e r . S c h m p . : 2 7 8 K (5 °C). A u s -b e u t e : 2 , 5 g ( 5 6 % ) .

C S H i t P (144 ,20)

B e r . C 66,64 H 1 1 , 8 8 , G e f . C 6 5 , 5 2 H 1 1 , 4 3 .

Cyclohexylfdimethyl)methylenphosphoran (5) 6,0 g (18 ,7 m m o l ) 2 w e r d e n m i t 100 m l T H F er-

h i t z t . K u r z v o r d e m S i e d e n d e s L ö s u n g s m i t t e l s w e r d e n m i t t e l s e i n e r F e s t s t o f f b i r n e 2 , 1 5 g ( 5 5 , l m m o l ) N a t r i u m a m i d z u g e g e b e n . N a c h ca. 1 h w e r d e n d i e S a l z e a b f i l t r i e r t u n d m i t e t w a s T H F a u s g e w a s c h e n . A u s d e m F i l t r a t w i r d d a s S o l v e n s e n t f e r n t u n d d e r R ü c k s t a n d i m V a k u u m d e s t i l l i e r t . F a r b l o s e F l ü s s i g -k e i t . S d p . : 3 3 3 K / 1 0 " 4 b a r (60 °C/0,1 T o r r ) . S c h m p . : 290 K (17 ° C ) ; f a r b l o s e N a d e l n . A u s b e u t e : 1 ,93 g ( 6 5 % ) .

C 9 H 1 9 P (168,23)

B e r . C 68,32 H 1 2 , 1 0 , G e f . C 6 7 , 8 5 H 12,04.

Cyclopentyl(trimethyl)phosphonium-chlorid (6)

0,47 g (3,2 m m o l ) 4 w e r d e n m i t 10 m l E t h e r v e r -d ü n n t u n d i m E i s b a d u n t e r R ü h r e n 10 m l 0,4 M e t h e r i s c h e C h l o r w a s s e r s t o f f l ö s u n g (4 m m o l ) z u g e -t r o p f t . D e r s o f o r t a u s f a l l e n d e N i e d e r s c h l a g w i r d n a c h 3 h a b f i l t r i e r t u n d a u s M e t h y l e n c h l o r i d u m -k r i s t a l l i s i e r t . F a r b l o s e s S a l z , d a s b e i 4 5 9 K (185 °C) s c h m i l z t . A u s b e u t e : 0 ,49 g ( 8 5 % ) .

C g H i g C l P (180,66)

B e r . C 5 3 , 1 9 H 10,04, G e f . C 5 3 , 5 1 H 1 0 , 1 5 .

1.6-Bis(dimethyl-methylen-phosphoranyl)hexan (7)

9,0 g (22,7 m m o l ) 3 w e r d e n i n 100 m l T H F s u s p e n -d i e r t u n d w i e v o r s t e h e n d m i t 2 ,64 g (67,7 m m o l ) N a t r i u m a m i d z u r R e a k t i o n g e b r a c h t . B e i d e r dest i l -l a t i v e n A u f a r b e i t u n g d e s P r o d u k t s e m p f i e h l t es s i c h , v o r g e w ä r m t e s „ K ü h l w a s s e r " z u v e r w e n d e n , d a 7 s o n s t i n d e r D e s t i l l e a u s k r i s t a l l i s i e r t . F a r b l o s e N a d e l n . S c h m p . : 3 4 3 K (70 °C). S d p . : 4 2 3 K / 1 0 - 4 b a r ( 1 5 0 °C/0,1 T o r r ) . A u s b e u t e : 3 ,29 g ( 6 2 % ) .

C12H28P2 (234,30) B e r . C 6 1 , 5 2 H 12 ,05 , G e f . C 6 0 , 7 5 H 1 1 , 9 4 .

Dimeres [Cyclopentylfmethyl)phosphonium-bis-methylido]gold(I) (8)

0 , 4 5 g (1 ,47 m m o l ) T r i m e t h y l p h o s p h i n g o l d ( I ) -c h l o r i d u n d 0,43 g (2,98 m m o l ) 4 e r g e b e n a n a l o g 0,23 g ( 8 7 % ) P h o s p h o n i u m s a l z 6 u n d d e n K o m -p l e x 8. F a r b l o s e N a d e l n , d i e b e i 4 9 6 K (223 °C) s c h m e l z e n ( D S C ) . A u s b e u t e : 0,47 g ( 9 4 % ) .

C16H32AU2P2 (680,31) B e r . C 28,25 H 4 , 7 4 A u 5 7 , 9 0 . G e f . C 28,35 H 4 , 7 8 A u 5 7 , 8 .

Polymeres [1.6-Bis(methylphosphonium-bis-methylido)hexyl]digold(I) (9)

0,38 g ( 1 , 1 2 m m o l ) T r i m e t h y l p h o s p h i n g o l d ( I ) -c h l o r i d u n d 0,60 g (2,56 m m o l ) 7 w e r d e n n a c h d e r w e i t e r o b e n b e s c h r i e b e n e n V o r s c h r i f t u m g e s e t z t . D e r a b g e t r e n n t e N i e d e r s c h l a g w i r d m i t M e t h a n o l g e w a s c h e n , w o b e i d a s P h o s p h o n i u m s a l z 3 i n L ö s u n g g e h t . D e r z u r ü c k b l e i b e n d e G o l d k o m p l e x 9 w i r d m i t P e n t a n g e w a s c h e n u n d g e t r o c k n e t . ( D i e b e n z o l i s c h e L ö s u n g e n t h ä l t n a c h A b z i e h e n d e s S o l v e n s k e i n i d e n t i f i z i e r b a r e s P r o d u k t . ) F a r b l o s e s P u l v e r . S c h m p . : 4 7 8 K (205 °C). A u s b e u t e : 0 , 1 8 g ( 4 7 % ) .

( C 1 2 H 2 6 A u 2 P 2 ) n (626,22)

B e r . C 23,02 H 4 , 1 8 , G e f . C 22,81 H 4 , 1 4 .

Geräte: D i f f e r e n t i a l k a l o r i m e t r i e P e r k i n E l m e r D S C 2 ; I n f r a r o t s p e k t r o s k o p i e P e r k i n E l m e r 5 7 7 ; M a s s e n s p e k t r o s k o p i e V a r i a n M A T C H 4 ; N M R -S p e k t r o s k o p i e V a r i a n E M 360, J e o l C - 6 0 H L , B r u -k e r X L 9 0 ; A t o m a b s o r p t i o n P y e U n i c a m S P 1900 ( P h i l i p s ) .

Aufstellung der NMB-Daten der Vorstufen und Derivate

1 : i H - N M R ( C F 3 C O O H , T M S i n t . ) : <5(CH3P) = 1 ,97 p p m , d . 9 H , 2 J ( P H ) = 1 4 , 1 H z ; <5(CH2Br) = 3 ,52, t , 2 H , 3 J ( H H ) = 6 , 2 ; <5(CH2)4 = 1 , 3 6 - 2 6 7 , m . 8 H . { 3 1 P } : s, t , m . - 3 i P - N M R ( C F 3 C O O H , H 3 P O 4 e x t . ) : <5(P) = 25 ,8 (s, { i H } ) .

2 : i H - N M R (wie o b e n ) : 6 ( C H 3 P ) = 2,00, d , 9 H . 2 J ( P H ) = 1 4 , 6 ; <KCH 2 Br) - 3 ,59, t , 2 H , 3 J ( H H ) = 6 , 7 ; <5(CH2)5 = 1 , 3 7 - 2 , 7 0 , m , 1 0 H . p P } : s, t , m . -3 1 P - N M R (wie o b e n ) : <5(P) = 25 ,6 , s, { i H } .

3 : i H - N M R (wie o b e n ) : <5(CH3P) = 2,00, d , 1 8 H , V ( P H ) = 1 4 , 6 : <5(CH2)6 = 1 , 4 2 - 2 , 7 0 , m , 1 2 H . { 3 1 P } : s, m . - 3 1 P - N M R (wie o b e n ) : <5(P) = 25 ,6 , s,

M .

6 : i H - N M R (wie o b e n ) : <5(CH3P) = 1 ,92, d , 9 H . 2 J ( P H ) = 1 3 , 9 ; <5(C5H9) = 1 , 3 2 - 2 . 9 6 (m, 9 H ) . P P } : s, m . - 3 1 P - N M R (wie o b e n ) : <5(P) = 2 9 , 7 , s, { X H}.

7 : i H - N M R ( B e n z o l , T M S i n t . ) : < 5 ( P = C H 2 ) = — 0 , 0 3 , d , 4 H , 2 J ( P H ) = 7 , 5 ; <5(CH3P) = 1 , 3 3 , d . 1 2 H , 2 J ( P H ) = 1 2 . 7 ; <5(CH2)6 = 1 , 1 3 - 1 , 2 0 . m , 1 2 H . P P } : s, s, m . - 1 3 C - { i H } - N M R ( B e n z o l - d 6 , T M S ) : < 5 ( P = C H 2 ) = — 5 , 5 5 . d , i J ( P C ) = 8 7 , 9 ; <5(PCH3) = 16 ,99, d , i J ( P C ) = 5 8 , 6 ; <5(P-CH2) = 32,96, d .

H. Schmidbaur-H. P. Scherm • Cycloalkyl-dimethyl - methy len -phosphorane 1351

1 J ( P C ) = 5 3 , 7 ; <5(C-2) = 30,8, d , 2 J ( P C ) = 1 4 , 6 ; (5(C-3) = 2 2 , 6 1 , s, i H - g e k o p p e l t : d t , i J ( C H ) = 1 4 7 , 7 ; d q , i J ( C H ) = 1 2 7 , 9 ; d t , V ( C H ) = 1 2 3 , 5 ; d t , ! J ( C H ) = 1 2 5 , 5 ; t , i J ( C H ) = 129,4. - 3 i P - N M R ( B e n z o l , H 3 P 0 4 e x t . ) : <5(P) = 4 ,5 , s, {^H}.

8 : i H - N M R (CH 2 C1 2 , T M S e x t . ) : 6 ( C H 3 P ) = 2,09, d , 2 J ( P H ) = 1 2 , 7 ; <5(CH2) = 1 , 6 5 ( v A ) u n d 1 , 3 1 ( v B ) , m , 2 J ( H H ) 9 ; 2 J ( P H ) = 1 4 , 6 ; <5(C5H9) = 1 , 7 2 - 3 , 0 6 ,

m . P P } : s, m ; A B . - 3 1 P - N M R ( B e n z o l , H 3 P 0 4

e x t . ) : Ö(P) = 40,5, s, { i H } .

U n s e r e A r b e i t e n w u r d e n i n d a n k e n s w e r t e r W e i s e u n t e r s t ü t z t v o n d e r D e u t s c h e n F o r s c h u n g s g e m e i n -s c h a f t , v o m V e r b a n d d e r C h e m i s c h e n I n d u s t r i e u n d - d u r c h C h e m i k a l i e n s p e n d e n - v o n d e r F a . H o e c h s t A G , W e r k K n a p s a c k .

[ 1 ] H . S c h m i d b a u r u n d H . P . S c h e r m , C h e m . B e r . 1 1 0 , 1 5 7 6 ( 1 9 7 7 ) .

[ 2 ] H . S c h m i d b a u r , H . P . S c h e r m u n d U . S c h u b e r t , C h e m . B e r . 1 1 1 , 7 6 4 ( 1 9 7 8 ) .

[ 3 ] R . K ö s t e r , M . A . G r a s s b e r g e r u n d D . S i m i c , L i e b i g s A n n . C h e m . 7 3 9 , 2 1 1 ( 1 9 7 0 ) .

[ 4 ] H . S c h m i d b a u r u n d R . F r a n k e , A n g e w . C h e m . 8 5 , 4 4 9 ( 1 9 7 3 ) ; A n g e w . C h e m . I n t , E d . E n g l . 1 2 , 4 1 6 ( 1 9 7 3 ) ; I n o r g . C h i m . A c t a 1 3 , 8 4 ( 1 9 7 5 ) .

[ 5 ] H . S c h m i d b a u r , J . R . M a n d l , W . R i c h t e r , V .

B e j e n k e , A . F r a n k u n d G . H u t t n e r , C h e m . B e r . 1 1 0 , 2 2 3 6 ( 1 9 7 7 ) ; H . S c h m i d b a u r , J . R . M a n d l , A . F r a n k u n d G . H u t t n e r , C h e m . B e r . 1 0 9 , 4 6 6 ( 1 9 7 6 ) .

[ 6 ] R . H u i s g e n , A n g e w . C h e m . 6 9 , 3 4 1 ( 1 9 5 7 ) . [ 7 ] F . C . M a r c h , R . M a s o n , K . M . T h o m a s u n d B . L .

S h a w , C h e m . C o m m u n . 1 9 7 5 , 5 8 4 ; A . J . P r y d e , B . L . S h a w u n d B . W e e k s , C h e m . C o m m u n . 1 9 7 3 , 9 4 7 .