The synthesis and reactivity of 16-electron half-sandwich iridium complexes bearing a carboranylthioamide ligand

Abstract

A 16-electron half-sandwich Ir(III) complex (Cp*Ir(SCN-Ph)C₂H₁₀H₁₁, 2) featuring an o-carboranylthioamidate ligand has been synthesized, and its reactivity has been studied in detail. 2 reacts with donor ligands to afford a stable 18-electron configuration. Interestingly, the electron-deficient iridium complex 2 underwent an Ir–S bond insertion reaction with DMAD to produce an acetylene insertion product 5. Complex 2 also reacted with the [Cp*Ir] unit, produced by the reaction between [Cp*IrCl₂]₂ and AgOTf, to form a unique binuclear species with a metal–metal bond. Moreover, a selective B(6)–H bond activation of the o-carborane complex has also been achieved.