Synthesis of Thiolato Heterometalllc Clusters from the Reaction of Os3(CO)9(NCMe)(μ‐H)(μ‐SMe) with CpW(CO)3H

Abstract

AbstractDecarbonylation of triosmium methylthiolato cluster Os3(CO)10(μ‐H)(μ‐SMe) with Me3NO in acetonitrile solution gave cluster Os3(CO)9(NCMe)(μ‐H)(μ‐SMe) (1), in which one axial CO on the non‐bridged Os atom is replaced by an acetonitrile ligand. Crystal data for 2: space group P bca, a = 14.491(1), b = 16.107(5), c = 16.639(5) Å, Z = 8; RF = 0.037, Rw = 0.033. Treatment of 2 with CpW(CO)3H in refluxing THF solution yielded two cluster compounds with formula CpWOs3(CO)11(μ‐H)2(μ3‐SMe) (2) and CpWOs3(CO)11(μ‐H)2(μ‐SMe) (3) as the principle products. The first possesses a spiked‐triangular geometry with a triply bridging thiolato ligand and the second adopts a butterfly metal core arrangement with an edge‐bridging thiolato grouping. The structure of 2 was characterized by single‐crystal X‐ray diffraction. Crystal data: space group P 1, a = 8.865(5), b = 8.959(3), c = 16.688(4) Å, α = 103.49(2), β = 93–58(3), γ = 113.03(4)°, Z = 2, RF = 0.034, Rw = 0.035.