Synthesis and structure of heterometallic complexes (RhFe, CoFe) containing bridging 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolato ligands

Abstract

The prototype hetero-binuclear complexes containing metal–metal bonds, {Cp′Rh[E₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (Cp′ = Cp* = η⁵-Me₅C₅, E = S(5a), Se(5b); Cp′ = Cp″ = η⁵-1,3-^tBu₂C₅H₃, E = S(6a), Se(6b)) and {Cp′Co[E₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (Cp′ = Cp* = η⁵-Me₅C₅, E = S(7a), Se(7b); Cp′ = Cp = η⁵-C₅H₅, E = S(8a), Se(8b)) were obtained from the reactions of 16-electron complexes Cp′Rh[E₂C₂(B₁₀H₁₀)] (Cp′ = Cp*, E = S(1a), Se(1b); Cp′ = Cp″, E = S(2a), Se(2b)), Cp′Co[E₂C₂(B₁₀H₁₀)] (Cp′ = Cp*, E = S(3a), Se(3b); Cp′ = Cp, E = S(4a), Se(4b)) with Fe(CO)₅ in the presence of Me₃NO. The molecular structures of {Cp*Rh[E₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (E = S(5a), Se(5b)), {Cp″Rh[S₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (6a) {Cp*Co[S₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (7a) and {CpCo[S₂C₂(B₁₀H₁₀)]}[Fe(CO)₃] (8a) have been determined by X-ray crystallography. All these complexes were characterized by elemental analysis and IR and NMR spectra.