Syntheses and structures of heterometallic clusters by the reaction of o-carboranyl cobaltadichalcogenolato complexes

Metalladichalcogenolate cluster complexes Cp'Co{E(2)C(2)(B(10)H(10))}]{Co2(CO)5} Cp' = eta5-C5H5, E = S(3a), E = Se(3b); Cp' = eta5-C5(CH3)5, E = S(4a), E = Se(4b)], {CpCoE(2)C(2)(B(10)H(10))]}(2)Mo(CO)2] E = S(5a), Se(5b)], Cp*Co(micro2-CO)Mo(CO)(py)2E(2)C(2)(B(10)H(10))] E = S(6a), Se(6b)], Cp*CoE(2)C(2)(B(10)H(10))]Mo(CO)2E(2)C(2)(B(10)H(10))] E = S(7a), Se(7b)], (Cp'CoE(2)C(2)(B(10)H(10))]W(CO)2 E(2)C(2)(B(10)H(10))] Cp' = eta5-C5H5, E = S(8a), E = Se(8b); Cp' = eta5-C5(CH3)5, E = S(9a), E = Se(9b)], {CpCoE(2)C(2)(B(10)H(10))]}(2)Ni E = S(10a), Se(10b)] and 3,4-(PhCN(4)S)-3,1,2-PhCN(4)SCo(Cp)S(2)]-3,1,2-CoC(2)B(9)H(8) 12 were synthesized by the reaction of Cp'CoE(2)C(2)(B(10)H(10))] Cp' = eta5-C5H5, E = S(1a), E = Se(1b); Cp' = eta5-C5(CH3)5, E = S(2a), E = Se(2b)] with Co2(CO)8, M(CO)3(py)3 (M = Mo, W), Ni(COD)2, Rh(COD)Cl]2, and LiSCN4Ph respectively. Their spectrum analyses and crystal structures were investigated. In this series of multinuclear complexes, 3a,b and 4a,b contain a closed Co3 triangular geometry, while in complexes 5a-7b three different structures were obtained, the tungsten-cobalt mixed-metal complexes have only the binuclear structure, and the nickel-cobalt complexes were obtained in the trinuclear form. A novel structure was found in metallacarborane complex 12, with a B-S bond formed at the B(7) site. The molecular structures of 4a, 5a, 6a, 7b, 9a, 9b, 10a and 12 have been determined by X-ray crystallography.