Insertion of nitrene and chalcogenolate groups into the Ir-C σ bond in a cyclometalated iridium(III) complex

Treatment of [Cp*Ir(ppy)Cl] (Cp* = eta(5)-C(5)Me(5), ppyH = 2-(2-pyridyl) phenyl) with Ag(OTf) (OTf = triflate) in MeOH and MeCN gave the solvento complexes [Cp*Ir(ppy)(solv)][OTf] (solv = MeOH (1) and MeCN (2)). Complex 1 is capable of catalyzing oxidation and azirdination of styrene with PhIO and PhINTs (Ts = tosyl), respectively. Treatment of 2 with a stoichiometric amount of PhINTs resulted in the insertion of the NTs group into the Ir-C(ppy) bond and formation of [Cp*Ir(eta(2)-ppy-NTs)(MeCN)][OTf] (3). Treatment of 1 with R(2)E(2) afforded [Cp*Ir(ppy)(eta(1)-R(2)E(2))][OTf] (E = S (4), Se (5), Te (6)). Reactions of 4 and 5 with Ag(OTf) resulted in cleavage of the E-E bond and insertion of an ER group into the Ir-C(ppy) bond. The crystal structures of complexes 2-6 and [Cp* Ir(eta(2)-ppy-S-p-tol)(H(2)O)][OTf](2) have been determined. (C) 2010 Elsevier B.V. All rights reserved.