117985-21-4Relevant articles and documents
Reactions of Cp2Fe2(CO)2(μ-CO)(μ-CSR)+ bridging-carbyne complexes with nucleophiles
Schroeder, Norman C.,Funchess, Robert,Jacobson, Robert A.,Angelici, Robert J.
, p. 521 - 529 (2008/10/08)
The bridging-thiocarbyne carbon in Cp2Fe2(CO)2(μ-CO)(μ-CSMe)+ (1) reacts with the nucleophiles RS- (R = Me, Ph, and Bz) and PhSe- to give the bridging-carbene complexes Cp2Fe2(CO)2(μ-CO)[μ-C(SMe)SR] (4-6) and Cp2Fe2(CO)2(μ-CO)[μ-C(SMe)SePh] (7). The PhS- and PhSe- groups in 5 and 7 migrate from the carbene carbon to an Fe with displacement of a CO group to give the carbyne complexes Cp2Fe2-(XPh)(CO)(μ-CO)(μ-CSMe), where X = S or Se. Treatment of the carbene complexes 4 and 5 with HBF4 results in the removal of a RS group to regenerate the cationic carbyne 1 and Cp2Fe2(CO)2(μ-CO)(μ-CSPh)+. The carbyne carbon in 1 is attacked by BzMgCl and BH4- to yield the carbene complexes Cp2Fe2(CO)2-(μ-CO)[μ-C(SMe)Bz] and Cp2Fe2(CO)2(μ-CO)[μ-C(SMe)H]. An X-ray diffraction structural investigation of this latter compound is reported. All of the bridging-carbene complexes are fluxional, and several isomers have been identified by their IR and NMR spectra. Reaction of 1 with 4-(dimethylamino)pyridine (4-DMAP) gives the CO-substituted carbyne Cp2Fe2(4-DMAP)(CO)(μ-CO)(μ-CSMe)+.
