Synthesis and characterization of two types of skeleton heterobimetallic trinuclear Mo(W)–Cu–S clusters containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane

Reactions of (NH4)2MS4 or (NH4)MOS3 (M = Mo, W) with CuSCN and the closo carborane diphosphine 1,2-(PPh2)2-1,2-C2B10H10 in CH2Cl2 yielded five heterobimetallic trinuclear Mo(W)–Cu–S clusters with the formula Cu2MS4L2 (M = Mo(1), W(3), L = 1,2-(PPh2)2-1,2-C2B10H10), Cu2MoS4L2 · CH2Cl2 (2) and Cu2MOS3L2 (M = Mo(4),W(5)). All the clusters have been characterized by elemental analysis, FT-IR, UV/Visible, 1H and 13C NMR spectroscopy and X-ray structure determination. X-ray crystal structure analysis showed that the metal skeleton of these clusters could be classified into two types. With (NH4)2MS4 (M = Mo, W), the three metal atoms (two Cu atoms and one M atom (M = Mo, W)) are almost in a linear conformation, while with (NH4)2MOS3 the conformation of the heterobimetallic trinuclear cluster core was a butterfly-shaped (or referenced as defective cubane-like with two corners missing). The coordination sphere of the metal atoms in all the clusters, either for Cu or M, should be described as a distorted tetrahedron. For each cluster, the closo carborane diphosphine ligand 1,2-(PPh2)2-1,2-C2B10H10 was introduced into the Cu2MS4 or Cu2MOS3 cluster cores and coordinated bidentately through the P atoms to Cu(I), and this resulted in a stable five-member chelating ring between the bis-diphosphine ligand and the metal.

A carborane skeleton was introduced into heterometallic sulfide cluster cores and five heterobimetallic trinuclear Mo(W)–Cu–S clusters with linear or butterfly-shaped skeletons containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane have been synthesized by the reactions of (NH4)2MS4 or (NH4)2MOS3 (M = Mo, W) with CuSCN and 1,2-(PPh2)2-1,2-C2B10H10 (L) in dichloromethane. The products have been characterized by elemental analysis, FT-IR, UV/Visible, 1H and 13C NMR spectroscopy and X-ray structure determination.Figure optionsDownload as PowerPoint slide