Magnesocene: Structure and Bonding

A. G. Pinkus
Baylor University
Waco, Texas 76703

Covalent or ionic?

A l t h o u g h the m o s t c o m m o n state o f c o o r d i n a t i o n for m a g n e s i u m i n i t s c o m p o u n d s is f o u r (1), e x a m p l e s o f t h r e e - ( 2 ) ,

f i v e - ( 3 ) , s i x - ( 4 ) , a n d e i g h t - c o o r d i n a t i o n ( 5 ) h a v e also b e e n
reported. A n unusual type of bonding for magnesium w h i c h
does n o t f i t i n t o a n y o f these categories occurs i n magnesoc e n e . M a g n e s o c e n e is a m e m b e r o f t h e g e n e r a l class o f o r g a n o m e t a l l i c c o m p o u n d s k n o w n as m e t a l l o c e n e s ( 6 ) o r
" s a n d w i c h " c o m p o u n d s o f w h i c h the f i r s t example t o be reco g n i z e d is t h e w e l l - k n o w n f e r r o c e n e . A l t h o u g h i t is g e n e r a l l y
agreed t h a t b o n d i n g i n metallocenes o f t r a n s i t i o n metis a p pears t o be p r e d o m i n a n t l y covalent, t h e n a t u r e o f b o n d i n g i n
m a g n e s o c e n e is c u r r e n t l y i n d i s p u t e . T h i s p a p e r w i l l p r e s e n t
a bref review o f t h e s t r u c t u r e s a n d b o n d i n g p r o p o s e d f o r
magnesocene leading u p t o the m o s t recent w o r k .
1

A l t h o u g h m a g n e s o c e n e was f i r s t p r e p a r e d ( 7 ) b y a d d i t i o n
of cyclopentadiene t o ethylmagnesium b r o m i d e a n d r e m o v i n g
e t h e r s o l v e n t i n v a c u o , i t c a n also b e p r e p a r e d (8) b y t h e r e action of metallic magnesium w i t h cyclopentadiene ( e q n .

(D).
2C H + Mg 6

H + Mg(C H )

(1)

M a g n e s o c e n e is a u s e f u l i n t e r m e d a t e f o r t h e p r e p a r a t i o n (9)
of other metallocenes either i n t h e m o l t e n state or i n s o l u t i o n
( e q n . ( 2 ) ) . T h e h i g h free e n e r g y o f f o r m a t i o n o f M g C l 2 f a v o r s
the

metathesis.

Mg(C H )2 + MC1 - M ( C H ) + MgCl

(2)
M a g n e s o c e n e has b e e n r e p o r t e d (10) t o h a v e b e e n p r e p a r e d
i n a rose-colored m o d i f i c a t i o n i n a d d i t i o n t o t h e b e t t e r - k n o w n
form.
W e i s s a n d F i s h e r (11) d e t e r m i n e d t h a t M g ( C H ) 2 i n t h e
crystalline state h a d a s a n d w i c h - l i k e s t r u c t u r e a n d proposed
weak covalent d s p h y b r i d i z a t i o n overlapping t h e ionic
electrostatic b i n d i n g between the m e t a l a n d cyclopentadienyl
ions. B a s e d o n m a g n e t i c , s p e c t r a l , a n d c h e m i c a l i n v e s t i g a t i o n s ,
W i l k i n s o n , C o t t o n , a n d B i r m i n g h a m (12) c o n c l u d e d t h a t i o n i c
b o n d i n g was present; t h e t w o c y c l o p e n t a d i e n i d e a n i o n s w o u l d
be e x p e c t e d o n e l e c t r o s t a t i c g r o u n d s t o a l i g n t h e m s e l v e s o n
o p p o s i t e sides o f t h e c a t i n w i t h p a r a l l e l p l a n e s a n d t o v e r y
closely resemble ferrocene. T h e concept o f ionic b o n d i n g i n
M g ( C s H ) 2 was f u r t h e r e l a b o r a t e d b y C o t t o n a n d R e y n o l d s
(13). L i p p i n c o t t , X a v i e r , a n d Steele (14) s t u d i e d t h e i n f r a r e d
a n d R a m a n spectra o f solutions a n d the solid state a n d i n
comparison w i t h studies o n ferrocene c o n f i r m e d the sandwich-type structure. However, they concluded that their results were not i n agreement w i t h the ionic b o n d i n g concept
b u t were better explained b y covalent r i n g - t o - m e t a l b o n d i n g
w h i c h was, however, weaker t h a n t h e m e t a l - t o - r i n g b o n d i n g
i n ferrocene. F r o m a gas-phase electrn d i f f r a c t i o n s t u d y ,
H a a l a n d , et al. (15,16),
d e t e r m i n e d t h a t the best agreement
b e t w e e n c a l c u l a t e d a n d e x p e r i m e n t a l i n t e n s i t i e s was o b t a i n e d
b y a s s u m i n g eclipsed C5H5 r i n g s (D
s y m m e t r y ) (see f i g u r e ) .
H o w e v e r , a m o d e l w i t h staggered s y m m e t r y (Z) ) c o u l d n o t
5

rt

5(

be c o n c l u s i v e l y r u l e d o u t . T h e y also c o n c l u d e d t h a t t h e r e was
n o s i g n i f i c a n t d e v i a t i o n f r o m p l a n a r i t y f o r t h e C5H5 r i n g s a n d
t h a t m a g n e s o c e n e is b e s t r e g a r d e d as a c o v a l e n t r a t h e r t h a n
an ionic compound.
M o r e r e c e n t l y , A l e k s a n y a n a n d c o w o r k e r s (17) o b t a i n e d
R a m a n a n d i n f r a r e d spectra o n t h e c o m p o u n d . R a m a n results
were f o r solid a n d m e l t forms a n d i n c l u d e d depolarization
measurements while i n f r a r e d data f o r the solid covered the
range 400-3200 c m . T h e i r analysis o f the data led t o the
c o n c l u s i n t h a t t h e M g - C p b o n d is m a i n l y i o n i c .
- 1

Literature Cited
(1) B a i l a r , J . C , Jr. in " T h e Chemistry o f t h e C o o r d i n a t i o n C o m p o u n d s , " (Editor:
Bailar,
J . C , J r . ) , R e i n h o l d , New Y o r k , 1956, p. 243.
(2) F o r a recent review: P i n k u s , A . G., Coord. Chem. Rev., 25, 173 (1978).
(3) S t u c k y , G., and R u n d l e , R. E., J . Amer. Chem. Soc, 86, 4821 (1964); V a l l i n o , M . , Organometal.
Chem., 20, 1 (1969).
(4) Schroder, F., and S p a n d a u , H . , Naturwissenschaften,
53, 360 (1966); Schrder, F. A.,
Chem. Ber., 102, 2035 (1969); A t w o o d , J . L . , a n d Stuckey, G. D . , J .
Organometal.
Chem., 13, 53 (1968); T o n e y , J . D . , a n d S t u c k y , G. D . , J . Organometal
Chem., 28,
5(1971).
(5) S h a n n o n , R. D . , and P r e w i t t , C. T . , Acta Cryst., B 2 5 , 9 2 5 (1969); M o r t i e r , W . J . , P l u t h ,
J . J . , a n d S m i t h , J . B . , Nature, 256, 718 (1975).
(6) Reviews dealing i n p a r t w i t h various aspects o f metallocenes (excluding ferrocenes):
(a) Pauson, P. L . , " C y c l o p e n t a d i e n y l M e t a l C o m p o u n d s " in " O r g a n o m e t a l l i c
C h e m i s t r y " , (Editor:
Zeiss, H . ) , R e i n h o l d , New Y o r k , 1960, C h a p . 7, p p . 346-379;
(b) Zeiss, H . , " A r e n e Complexes o f t h e T r a n s i t i o n M e t a l s " i n ibid., C h a p . 8, p p .
380-425. (c) B i r m i n g h a m , C. M - , "Synthesis o f Cyclopentadienyl M e t a l Compounds,"
in " A d v a n c e s i n Organometallic C h e m i s t r y , " V o l . 2, ( E d i t o r s : Stone, F . G . A., and
West, R.) A c a d e m i c Press, N e w Y o r k , 1964, p p . 365-413; (d) C h u r c h i l l , M . R., a n d
Masn, R., " T h e S t r u c t u r a l Chemistry o f Organo-Transition M e t a l Complexes: Some
Recent D e v e l o p m e n t s , " ibid., v o l . 5, 1967, p p . 9 3 - 1 3 5 ; (e) Cais, M . , a n d L u p i n , M .
S., " M a s s Spectra o f Metallocenes & Related C o m p o u n d s , " ibid., v o l . 8, 1970, p p .
211-333; (f) S l o c u m , D . W., and E r n s t , C. R., " E l e c t r o n i c Effects i n Metallocenes
and C e r t a i n Related Systems," ibid., v o l . 10, 1972, p p . 79-114; (g) B r u c e , M . I . ,
" O r g a n o - T r a n s i t i o n M e t a l C h e m i s t r y - A G u i d e t o t h e L i t e r a t u r e 1950-1970," ibid.,
vol. 10, pp. 273-346; (h) Rubezhov, A . Z. a n d G u b i n , S. P., " L i g a n d S u b s t i t u t i o n i n
T r a n s i t i o n M e t a l x - C o m p l e x e s , " ibid., v o l . 10, p p . 347-417; ( i ) Bruce, M . I . , " T h e
L i t e r a t u r e of O r g a n o - T r a n s i t i o n M e t a l C h e m i s t r y 1 9 7 1 , " ibid., v o l . 11,1973, pp. 447
ff; (j) B r u c e , M . I . , " T h e L i t e r a t u r e o f Organo T r a n s i t i o n M e t a l C h e m i s t r y 1972,"
ibid., v o l . 12, 1974, pp. 379-407; ( k ) S i l v e r t h o r n , W . E., " A r e n e T r a n s i t i o n M e t a l
C h e m i s t r y , " i b i d . , v o l . 13, 1975, p p . 47-137; (1) Razuvaev, G. A., a n d L a t y a e v a , V .
N . , " C o v a l e n t Organometallic C o m p o u n d s o f the T r a n s i t i o n M e t a l s , " Russ.
Chem.
Reo. 34, 251-267 (1965); Uspekhi Khim.,
p p . 585 f f ; ( m ) R y b i n s k a y a , M . I . , a n d
K o r n e v a , L . M . , " E l e c t r o p h i l i c S u b s t i t u t i o n i n C y c l o p e n t a d i e n i d e A n i o n s , " ibid.,
4 0 , 2 4 7 - 2 5 5 (1971); Uspekhi Khim, p p . 444 ff; ( n ) Leonova, E. V . , a n d K o c h e t k o v a ,
N . S., ibid., 4 2 , 2 7 8 - 2 9 2 (1973); Uspekhi Khim., p p . 615 ff; (o) B r a t e r m a n , P. S., and
Cross, R. J . , " O r g a n o - T r a n s i t i o n - m e t a l complexes: S t a b i l i t y , R e a c t i v i t y a n d O r b i t a l
Correlations," Chem. Soc. Reo., 2, 271 (1973); (p) H u n t , C. B . , Educ. Chem., 14,110
(1977).
(7) W i l k i n s o n , G., a n d C o t t o n , F. A., Chem. Ind., ( L o n d o n ) , 307 (1954); see also Fischer,
E. O., and H a f n e r , W . , Z. Naturforsch.,
9b, 503 (1954).
(8) B a r b e r , W . A., Inorg. Synth.,
6 , 1 1 (1960).
(9) H u l l , H . S., R e i d , A . F., a n d T u r n b u l l , A . G., Inorg. Chem., 6, 805 (1967) a n d refs.
therein.
(10) A l e k s a n y a n , V . T . , and L o k s h i n , B . V . , J . Organometal.
Chem., 131,113 (1977); A l e k sanyan, V . T . , L o k s h i n , B . V . , B o r i s o v , G . K . , D e v y a t y c h , G. G., N a g a r o v a , R. G.,
S m i r n o v , A . S., K o n i n g s t e i n , J . A . , a n d Gchter, B . F-, J . Organometal.
Chem., i n
press.
(11) Weiss, E., a n d Fisher, E. O., Z. Anorg. Allg. Chem., 278, 219 (1955).
(12) W i l k i n s o n , G., C o t t o n , F. A., and B i r m i n g h a m , J . M . , J . Inorg. Nuclear Chem., 2 , 9 5
(1956).
(13) C o t t o n , F. A., and Reynolds, L . J . , J . Amer. Chem. Soc, 80, 269 (1958).
(14) L i p p i n c o t t , E. R., X a v i e r , J . , and Steele, D.,J.Amer.
Chem. Soc., 83, 2262 (1961).
(15) H a a l a n d , A., L u s z t y k , J . , N o v a k , D . P., B r u n v o l l , J . , a n d Starowieyski, K . B . , J . Chem.
Soc, Chem. Comm., 54 (1974).
(16) H a a l a n d , A., L u s z t y k , J . , B r u n v o l l , J . , and Starowieyski, K . B . , J . Organometal.
Chem.,
85, 279 (1975).
(17) A l e k s a n y a n , V , T . , Garbuzova, I . A . , G a v r i l e n k o , V . V . , a n d Z a k h a r k i n , L . I . , J . Organometal.
Chem., 129, 139 (1977).

Chemical Abstracts nomenclature, from 1974 to the present date

for this compound is bis(r) -2,4-cyclopentadien-l-yl)magnesium. I n
earlier references the compound is variously named: bis(cyclopentadienyl)magnesium, (also bis-cyclopentadienylmagnesium), dicyclopentadienylmagnesium, di-ir-cyclopentadienylmagnesium and
magnesium cyclopentadienide. I n the present paper, this compound
w i l l be referred to by its t r i v i a l ame, magnesocene, for space-saving
brevity.
l

2.008

s i de view
1.423A

(rings

Structure of magnesocene (15, 16).

704

/ Journal

of Chemical

Education

perpendicular)