Chemistry of the paramagnetic Co3 (CO)9(μ3-S) cluster. Rational synthesis of Co3(CO)7(μ-X)(μ3-S) complexes

Article abstract of DOI:10.1021/om980147n

The paramagnetic Co₃(CO)₉(μ₃-S) cluster (1) reacts with organic compounds containing S-H, S-S, or P-H bonds to give diamagnetic Co₃(CO)₇(μ-X)(μ₃-S) (μ-X = (μ-L, μ-(1,2-η)-L, and μ-(1,3-η)-L) complexes. The reaction was used to prepare the derivatives with μ-L = SR (2a-h; R = Et, t-Eu, CH₂Ph, allyl, Ph, C₆F₅, 2-naphthyl, CH₂CH₂OH) and PPh₂ (7), μ-(1,2-η)-L = P(S)Ph₂ (8), and μ-(1,3-η)-L = S₂CR(R = SMe (4), OMe (5), Ph (6)). The reaction results in an increase of the oxidation state of cobalt and may be therefore called an oxidative substitution. It is the first successful and rational way to prepare derivatives of Co₃(CO)₉-(μ₃-S), a fundamental cluster molecule described in 1961. The crystal structures of the triphenylphosphine-substituted derivative of 2b, Co₃(CO)₄(PPh₃) ₃(μ-S-t-Bu)(μ₃-S) (3), and of 4, 6, and 8 were determined. A new, high-yield synthesis of 1 is described.