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

摘要

Metalladichalcogenolate cluster complexes [Cp'Co{E2C2(B10H10)}]{Co-2(CO)(5)} [Cp' = eta(5)- C5H5, E = S(3a), E = Se(3b); Cp' = eta(5)- C-5(CH3)(5), E = S( 4a), E = Se( 4b)], {CpCo[E2C2(B10H10)]}(2)Mo(CO)(2)] [ E = S(5a), Se( 5b)], Cp* Co(mu(2)-CO) Mo(CO)(py)(2)[E2C2(B10H10)] [E = S( 6a), Se( 6b)], Cp* Co[E2C2(B10H10)] Mo(CO)(2)[E2C2(B10H10)] [E = S( 7a), Se( 7b)], (Cp'Co[E2C2(B10H10)] W(CO)(2) [E2C2(B10H10)] [Cp' = eta(5)-C5H5, E = S(8a), E = Se(8b); Cp' = eta(5)-C-5(CH3)(5), E = S(9a), E = Se(9b)], {CpCo[E2C2(B10H10)]}(2)Ni [E = S(10a), Se(10b)] and 3,4-(PhCN4S)- 3,1,2-[PhCN4SCo(Cp)S-2]3,1,2- CoC2B9H8 12 were synthesized by the reaction of [Cp'CoE2C2(B10H10)] [Cp' = eta(5)-C5H5, E = S(1a), E = Se(1b); Cp' = eta(5)-C-5(CH3)(5), E = S(2a), E = Se( 2b)] with Co-2(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 Co-3 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.