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

The prototype hetero-binuclear complexes containing metal-metal bonds, {CpRhE2C2(B10H10)]}Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(5a), Se(5b); Cp = Cp = eta 5-1,3-tBu2C5H3, E = S(6a), Se(6b)) and {CpCoE2C2(B10H10)]}Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(7a), Se(7b); Cp = Cp = eta 5-C5H5, E = S(8a), Se(8b)) were obtained from the reactions of 16-electron complexes CpRhE2C2(B10H10)] (Cp = Cp*, E = S(1a), Se(1b); Cp = Cp, E = S(2a), Se(2b)), CpCoE2C2(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*RhE2C2(B10H10)]}Fe(CO)3] (E = S(5a), Se(5b)), {CpRhS2C2(B10H10)]}Fe(CO)3] (6a) {Cp*CoS2C2(B10H10)]}Fe(CO)3] (7a) and {CpCoS2C2(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.