Gold(I) Complexes with the <i>nido</i>-Diphosphino Ligand [7,8-(Ph<sub>2</sub>P)<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>]<sup>-</sup>. Preparation of the First Metallocarborane Complex of this Ligand. Crystal Structures of [Au{(PPh<sub>2</sub>)<sub>2</sub>C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>}(PPh<sub>3</sub>)]·CH<sub>2</sub>Cl<sub>2</sub> and [Au<sub>2</sub>{(PPh<sub>2</sub>)<sub>2</sub>C<sub>2</sub>B<sub>9</sub>H<sub>10</sub>}<sub>2</sub>{(PPh<sub>2</sub>)<sub>2</sub>(CH<sub>2</sub>)<sub>3</sub>}]·3Me<sub>2</sub>CO
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The reaction of [AuCl(PR3)] with [1,2-(Ph2P)2-1,2-C2B10H10] in refluxing ethanol proceeds with partial degradation (removal of a boron atom adjacent to carbon) of the closo species to give [Au{(PPh2)2C2B9H10}(PR3)] [PR3 = PPh3 (1), PPh2Me (2), PPh2(4-Me-C6H4) (3), P(4-Me-C6H4)3 (4), P(4-OMe-C6H4)3 (5)]. Similarly, the treatment of [Au2Cl2(μ-P-P)] with [1,2-(Ph2P)2-1,2-C2B10H10] under the same conditions leads to the complexes [Au2{(PPh2)2C2B9H10}2(μ-P-P)] [P-P = dppe = 1,2-bis(diphenylphosphino)ethane (6), dppp = 1,3-bis(diphenylphosphino)propane (7)], where the dppe or dppp ligands bridge two gold nido-diphosphine units. The reaction of 1 with NaH leads to removal of one proton, and further reaction with [Au(PPh3)(tht)]ClO4 gives the novel metallocarborane compound [Au2{(PPh2)2C2B9H9}(PPh3)2] (8). The structure of complexes 1 and 7 have been established by X-ray diffraction. [Au{(PPh2)2C2B9H10}(PPh3)] (1) (dichloromethane solvate) crystallizes in the monoclinic space group P21/c, with a = 17.326(3) Å, b = 20.688(3) Å, c = 13.442(2) Å, β = 104.710(12)°, Z = 4, and T = −100 °C. [Au2{(PPh2)2C2B9H10}2(μ-dppp)] (7) (acetone solvate) is triclinic, space group P1̄, a = 13.432(3) Å, b = 18.888(3) Å, c = 20.021(3) Å, α = 78.56(2)°, β = 72.02(2)°, γ = 73.31(2)°, Z = 2, and T = −100 °C. In both complexes the gold atom exhibits trigonal planar geometry with the 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate(1−) acting as a chelating ligand.
