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

Decarbonylation of triosmium methylthiolato cluster Os 3 (CO) 10 (μ‐H)(μ‐SMe) with Me 3 NO in acetonitrile solution gave cluster Os 3 (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; R F = 0.037, R w = 0.033. Treatment of 2 with CpW(CO) 3 H in refluxing THF solution yielded two cluster compounds with formula CpWOs 3 (CO) 11 (μ‐H) 2 (μ 3 ‐SMe) ( 2 ) and CpWOs 3 (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, R F = 0.034, R w = 0.035.