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

A 16-electron half-sandwich Ir(iii) complex (CpIr(SCN-Ph)CHH, 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 [CpIr] unit, produced by the reaction between [Cp*IrCl] 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.