Transition metal-cyanocarbon chemistry. IX. Reactions of monocyanoacetylene with dicarbonylcyclopentadienylmethylthiolatoiron(II). Crystal structures of 5-C5H5)(CO)> and of 2-Fe(CC-CN)(η5-C5H5)(C

Article abstract of DOI:10.1016/0022-328X(89)87215-8

The reaction of 5-C5H5)(SCH3)(CO)2> with monocyanoacetylene (HCCCN) in THF at room temperature gives the acetylide 5-C5H5)(CO)2> (1), the acylic species 5-C5H5)(CO)> (2), the binuclea

Full text of DOI:10.1016/0022-328X(89)87215-8

143
Journal of Organometallic Chemistry, 367 (1989)143-160
ElsevierSequoiaS.A.,Lausanne - Printed in The Netherlands
JOM 09735
Transition metai-cyanocarbon chemistry
IX *. Reactions of monocyanoacetylene
with dicarbonylcydopentadienylmethylthiolatoiron(II). Crystal
structures of [FeC(O)C(CN)=CH(SCH 3)( ~S-CsH s)(CO)I
and of [p-~2-Fe(C=:--C-CN)(T/s-CsHs) (CO) ~][Co(CO) 3]2
R. Kergoat *, M.M. Kubicki, L.C. Comes de Lima, H. Scordia, J.E. Guerchais
Unitd Associde au CNRS, No. 322, Chimie, Electrochimie et Photochimie Moldculaires, Equipe de Chimie
Inorganique Moldculaire, Universitd de Bretagne Occidentale, 29287 Brest, Cedex (France)
and P. L'Haridon
Unitd Associde au CNRS, No. 254, Laboratoire de Chimie Mindrale C, Universitd de Rennes Beaulieu,
35042 Rennes, Cedex (France)
(ReceivedNovember12th, 1988)
Abstract
The reaction of [Fe(~5-CsHs)(SCHa)(CO)2] with monocyanoacetylene
(HC=:-CCN) in THF at room temperature gives the acetylide [Fe(C=-CCNX~/s-
Cs H s)(CO) 2] (1), the acylic species [FeC(O)C(CN)--CH(SCH 3)(~S-Cs H s )(CO)] (2),
the binuclear complex [Fe(,/5-C5H 5)(CO) 2C(CN)=C(SCH a)Fe(7/5-C5H~ )(CO) 2] (3),
and the disubstituted olefin Z-(NC)CH--CH((SCH3) (4). If the HC=:-CCN is con-
densed on to a frozen solution of the thiolato complex and the mixture then allowed
to warm up, the acylic compound 2 is not isolated. Irradiation of I and 3 in the
presence of PPh 3 in THF gives the substituted complex [Fe(C~-CCN)(T/S-
CsHs)(CO)(PPh 3)] (6) and [Fe(7/5-C5H s)(CO) 2C(CN)=C(SCH 3)Fe(~/~-CsH5)(CO)-
(PPh3)] (10). Cycloaddition of tetracyanoethylene on 1 and 6 gives the correspond-
ing complexes [Fe(C=C(CN)C(CN)2CJ(CN)2(~/~-C~ H~ )(CO)(L)] (L = CO (7) or PPh 3
(8)). Under UV irradiation 8 is converted into Fe(~/3-C(CN)2C(CN)(~==C(CN)2)(T/5-
CsHs)(PPh3)] by loss of CO. Complex 1 reacts with Co2(CO)8 to form the
[p-~/2,Fe(C=-C-CN)(T/5-CsHs)(CO)2][Co(CO)3]2 (5). The structures of 2 and 5 have
been determined by X-ray diffraction.
* Part VIII: M. Etienne and J.E. Guerchais, submitted.
0022-328X/89/$03.50
© 1989ElsevierSequoiaS.A.