Synthesis and Crystal Structure of Three Carborane Complexes, [M{7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 } 2 ] (M = Cu, Zn) and [Ni(thf){7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 } 2 ]·thf, and Two Carborane Compounds, 1‐(OPPh 2 )‐2‐(PPh 2 )‐1,2‐C 2 B 10 H 10 and H[7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 ]·0.25C 2 H 5 OH

Three new carborane complexes containing the bis(phosphoryl)‐ nido ‐carborane ligand, [Cu{7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 } 2 ] ( 1 ), [Zn{7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 } 2 ] ( 2 ), and [Ni(thf){7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 } 2 ] · thf ( 3 ), were synthesized by the reactions of 1,2‐(PPh 2 ) 2 ‐1,2‐C 2 B 10 H 10 with CuCl 2 · 2H 2 O, ZnCl 2 , and NiCl 2 · 6H 2 O, respectively, in ethanol in air. Two other compounds, 1‐(OPPh 2 )‐2‐(PPh 2 )‐1,2‐C 2 B 10 H 10 ( 4 ) and H[7,8‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 ] · 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, 1 H and 13 C 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‐(OPPh 2 ) 2 ‐7,8‐C 2 B 9 H 10 ] – 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 OPPh 2 groups and one additional one from a thf molecule. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)