SYNTHESES AND REACTIONS OF DINUCLEAR MU-METHYLTHIOLATE ORGANOMETALLICCOMPLEXES

Products from reactions between [CpM(CO)(2)](2) (M = Fe, Ru) and [Me(2 )SSMe]BF4 depend on the ratio of reactants, reaction time, and solvent . Two organometallic products, [Cp(2)M(2)(CO)(4)(mu-SMe)]BF4 and [CpM( CO)(2)(SMe(2))]BF4 are generally formed. A proposed mechanism for this reaction involves initial addition of an SMe(+) group to the bimetall ic complex, followed by displacement of a CpM(CO)(2) moiety by L (L = Me(2)S, CpM(CO)(2)SMe, or solvent). The reaction of [Me(2)SSMe]BF4 wit h a mixture of [CpFe(CO)(2)](2) and [MeCpFe(CO)(2)](2), which gives a statistical mixture of the possible thiolate-bridged species, is accom modated by this mechanism. Alternative syntheses of [cp(2)M(2)(CO)(4)( mu-SMe)]BF4 (cpM = CpFe, MeCpFe, CpRu) and [CpFe(CO)(2)(mu-SMe)M(CO)(2 )cp]BF4 from [CpFe(CO)(2)(THF)]BF4 and cpM(CO)(2)SMe (cpM = MeCpFe, Cp Ru) provided pure samples of the thiolate-bridged complexes. Photolyse s of these complexes result in formation of [CpFe(CO)(mu-SR)(mu-CO)M(C O)Cp]BF4 (M = Fe, Ru).