Synthesis of mixed-metal clusters by the reaction of the unsaturated cluster [Os3(µ-H)2(CO)10] with transition-metal hydrides: the X-ray crystal structures of [Os3H3(CO)10{Cu(PPh3)}] and [Os3H3(CO)11{Ir(PPh3)}]

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Abstract
The co-ordinatively unsaturated dihydride cluster [Os3(µ-H)2(CO)10] reacts with the transition-metal hydrides [{CuH(PPh3)}6], [IrH(CO)2(PPh3)2], [RhH(CO)(PPh3)2], and [NiH(Cl)({P(C6H11)3}2] to give the mixed-metal clusters [Os3H3(CO)10{Cu(PPh3)}](1), [Os3H3(CO)11{Ir(PPh3)}](2), [Os3H3(CO)11{Rh(PPh3)}](3), and [Os3H2(CO)10{Ni[P(C6H11)3]}](4). These complexes have been characterized by i.r. and n.m.r. spectroscopy, and the structures of (1) and (2) have been established by single-crystal X-ray analysis. In complex (1) the three Os atoms lie at the vertices of an isosceles triangle the long edge [3.026(3)Å] of which is bridged by the Cu atom of the Cu(PPh3) ligand. The hydrides were not located directly but evidence suggests that they bridge the long Os–Os bond and the two Os–Cu bonds. The carbonyl arrangement is similar to that observed in [Os3H2(CO)10]. In complex (2) the Ir atom caps the Os3 triangle to form a distorted tetrahedral metal framework. The three Ir–Os bond lengths [2.759(3), 2.789(2), and 2.917(3)Å] show considerable variation. The distribution of the eleven terminal carbonyl ligands and the phosphine group, which is co-ordinated to the Ir atom, indicates that the three hydrides bridge the two longer Os–Os bonds, and the longest Os–Ir bond. From the spectroscopic data the overall geometry of complex (3) is closely related to that of (2), while (4) has a tetrahedral metal arrangement with hydrides and carbonyl groups bridging Os–Os and Os–Ni edges.

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