Journal of Organometallic Chemistry p. 157 - 164 (1996)
Update date:2022-08-03
Topics:
Treichel
Rublein
Products from reactions between [CpM(CO)2]2 (M = Fe, Ru) and [Me2SSMe]BF4 depend on the ratio of reactants, reaction time, and solvent. Two organometallic products, [Cp2M2(CO)4(μ-SMe)]BF4 and [CpM(CO)2(SMe2)]BF4 are generally formed. A proposed mechanism for this reaction involves initial addition of an SMe+ group to the bimetallic complex, followed by displacement of a CpM(CO)2 moiety by L (L = Me2S, CpM(CO)2SMe, or solvent). The reaction of [Me2SSMe]BF4 with a mixture of [CpFe(CO)2]2 and [MeCpFe(CO)2]2, which gives a statistical mixture of the possible thiolate-bridged species, is accommodated by this mechanism. Alternative syntheses of [cp2M2(CO)4(μ-SMe)]BF4 (cpM = CpFe, MeCpFe, CpRu) and [CpFe(CO)2(μ-SMe)M(CO)2cp]BF4 from [CpFe(CO)2(THF)]BF4 and cpM(CO)2SMe (cpM = MeCpFe, CpRu) provided pure samples of the thiolate-bridged complexes. Photolyses of these complexes result in formation of [CpFe(CO)(μ-SR)(μ-CO)M(CO)Cp]BF4 (M = Fe, Ru).
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