Syntheses and reactions of dinuclear μ-methylthiolate organometallic complexes

Article abstract of DOI:10.1016/0022-328X(95)05951-K

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).