Synthesis and characterization of the sterically hindered iridium(III) silyl complex:: (Et3P)3(H)2Ir[Si(H)Cl(C6H3-Mes2-2,6)] and the generation of the cationic iridium(III)-silylene complex:: [(Et3P)3(H)2Ir=Si(H)(C6H3-Mes2-2,6)][B(C6F5)4]

The oxidative addition reaction of (Et3P)(3)IrCl with H3Si(C6H3-Mes(2)-2,6) (Mes = 2,4,6-trimethylphenyl) affords the sterically hindered iridium(III)-silyl complex (Et3P)(3)(H)(2)Ir[Si(H)Cl(C6H3-Mes(2)-2,6)] (1) via a H/Cl exchange reaction at silicon. Complex 1 is characterized by H-1-, C-13-, P-31-, and Si-29-NMR and IR spectroscopy. The solid state structure of 1 is determined by X-ray crystallography. Complex 1 undergoes a halide abstraction reaction with LiB(C6F5)(4)(OEt2) to afford the cationic iridium(III)silylene complex [(Et3P)(3)(H)(2)Ir = Si(H)(C6H3-Mes(2)-2,6)][B(C6F5)(4)] (4). Complex 4 is characterized by H-1-, C-13-, P-31-, and Si-29-NMR spectroscopy. (C) 2002 Elsevier Science B.V. All rights reserved.