Abstract
The potential of [IrCl4(PMe2Ph2] as a one-electron oxidising agent in organometallic chemistry has been evaluated. In complementary redox reactions with metallocenes, salts of the general form [M(η-C5H5)2][IrCl4(PMe2Ph)2](1) are formed. In non-complementary reactions with platinum(0) and palladium(II) complexes some interesting mixed-metal mixed-valence complexes of the type [Ph3P)2Pt(µ-Cl)2IrCl2(PMe2Ph)2][IrCl4(PMe2Ph)2](2) and [(Me3As)ClPd(µ-Cl)2IrCl2(PMe2Ph)2](3) are formed. Complex (3) has been characterised by single-crystal X-ray diffraction studies. It crystallises in the space group P21/n of monoclinic symmetry in a cell of dimensions a= 12.218(2), b= 13.187(2), c= 17.832(2)A, β= 91.80(1)° and Z= 4, the final R and R′ being 0.046 and 0.051 respectively based on full-matrix refinement of 167 variables and 4 273 observations. This structural determination confirms that (3) contains an octahedral iridium(III) unit linked to a square-planar palladium fragment by means of chloride bridges.
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