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

Abstract

Metalladichalcogenolate cluster complexes [Cp′Co{E₂C₂(B₁₀H₁₀)}]{Co₂(CO)₅} [Cp′ = η⁵-C₅H₅, E = S(3a), E = Se(3b); Cp′ = η⁵-C₅(CH₃)₅, E = S(4a), E = Se(4b)], {CpCo[E₂C₂(B₁₀H₁₀)]}₂Mo(CO)₂] [E = S(5a), Se(5b)], Cp*Co(µ₂-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′ = η⁵-C₅H₅, E = S(8a), E = Se(8b); Cp′ = η⁵-C₅(CH₃)₅, E = S(9a), E = Se(9b)], {CpCo[E₂C₂(B₁₀H₁₀)]}₂Ni [E = S(10a), Se(10b)] and 3,4-(PhCN₄S)-3,1,2-[PhCN₄SCo(Cp)S₂]-3,1,2-CoC₂B₉H₈12 were synthesized by the reaction of [Cp′CoE₂C₂(B₁₀H₁₀)] [Cp′ = η⁵-C₅H₅, E = S(1a), E = Se(1b); Cp′ = η⁵-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.