Synthesis of Cp* Iridium and Rhodium Complexes Containing Bidentate sp 2 ‐N‐Donor Ligands and Counter‐Anions [Cp*MCl 3 ] –

Complexes of the type [Cp*MCl(N–N)][X] (M = Rh and Ir) have been synthesised, where N–N is a series of bidentate ligands with sp 2 N‐donors: bis(pyrazol‐1‐yl)methane (bpm), bis(1‐methylimidazol‐2‐yl)methane (bim), bis(3,5‐dimethylpyrazol‐1‐yl)methane (dmbpm), bis(1‐methylimidazol‐2‐yl) ketone (bik), bis(2,4,6‐trimethylphenylimino)acenapthene (mesBIAN), 2,4,6‐trimethylphenylimino‐(1‐methyl‐2‐imidazolyl)methane (mesim–mim), and X = Cl – , BF 4 – and the unusual anion [Cp*MCl 3 ] – . All of these complexes were synthesised by treatment of [Cp*MCl 2 ] 2 with 2 equivalents of ligand and were isolated as air stable solids. The solid‐state structures of [Cp*MCl(bpm)][Cp*MCl 3 ] (M = Rh and Ir) and [Cp*IrCl(bim)][Cp*IrCl 3 ] have been determined by single‐crystal X‐ray diffraction analysis. All of the structures of the bimetallic species displayed a “piano stool” configuration about the both the anionic and cationic metal centre. The solid‐state structures of the monometallic iridium species [Cp*IrCl(N–N)][BF 4 ], where N–N = bim, mesBIAN, and mesim‐mim, were also determined using single‐crystal X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)