Synthesis and crystal structure of three carborane complexes, [M{7,8-(OPPh2)(2)-7,8-C2B9H10}(2)] (M = Cu, Zn) and [Ni(thf){7,8-(OPPh2)(2)-7,8-C2B9H10}(2)]center dot thf and two carborane compounds, 1-(OPPh2)-2-(PPh2)-1,2-C2B10H10 and H[7,8-(OPPh2)(2)-7,8-C2B9H10]-0.25C(2)H(5)OH

Three new carborane complexes containing the bis(phosphoryl)-nido-carborane ligand, [Cu{7,8-(OPPh2)(2)-7,8-C2B9H10}(2)] (1), [Zn{7,8-(OPPh2)(2)-7,8-C2B9H10}(2)] (2), and [Ni(thf){7,8(OPPh2)(2)-7,8-C2B9H10}(2)]center dot thf (3), were synthesized by the reactions of 1,2-(PPh2)(2)-1,2-C2B10H10 with CuCl2 center dot 2H(2)O, ZnCl2, and NiCl2 center dot 6H(2)O, respectively, in ethanol in air. Two other compounds, 1-(OPPh2)-2-(PPh2,)-1,2-C2B10H10 (4) and H[7,8-(OPPh2)(2)-7,8-C2B9H10]center dot 0.25C(2)H(5)OH (5), were also obtained through the oxidation of the closo ligand in air. All new compounds were characterized by elemental analysis, FT-IR, H-1 and C-13 NMR spectroscopy, and single-crystal X-ray diffraction. In complexes 1 and 2, the metal atoms are coordinated to the four oxygen atoms of the two bidentate bis(phosphoryl) ligands [7,8-(OPPh2)(2)-7,8-C2B9H10](-) and adopt a square-planar geometry. For complex 3, the molecular structure reveals that the geometry at the nickel atom is square-pyramidal, with four oxygen atoms from the four OPPh2 groups and one additional one from a thf molecule. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).