A facile and general approach to the Rh-M (M = Co, Rh) single bond supported by ortho-carborane-1,2-dichalcogenolato ligands

A series of hetero- and homo-dinuclear complexes with direct metal-metal interaction are synthesized through reaction of Cp*Rh[E(2)C(2)(B(10)H(10))] (E = S (1a), Se (1b)) and CpRh[S(2)C(2)(B(10)H(10))] (2a) with low valent half-sandwich CpCo(CO)(2) or CpRh(C(2)H(4))(2) under moderate conditions. The resulting products, namely (Cp*Rh)(CpCo)[E(2)C(2)(B(10)H(10))] (E = S(3a); Se(3b)), (Cp*Rh)(CpRh)[E(2)C(2)(B(10)H(10))] (E = S(4a); Se(4b)) and (CpRh)(CpRh)[S(2)C(2)(B(10)H(10))] (5a), are fully characterized by IR and NMR spectroscopy and elemental analysis. The molecular structures of 3a, 3b, 4a, 4b and 5a are established by X-ray crystallography analyses, and the Rh-Co (2.4778(11) (3a) and 2.5092(16) (3b) A) and Rh-Rh bonds (2.5721(8) (4a), 2.6112(10) (4b), 2.5627(10) (5a) A) fall in the range of single bonds.