Two-Site O-H Addition to an Iridium Complex Featuring a Nonspectator Tricoordinate Phosphorus Ligand.

The synthesis and reactivity of an ambiphilic iridium complex IrCl(PPh)() (; = P(N(-N(2-pyridyl)CH))) featuring a chelating nontrigonal phosphorus triamide ligand is reported. The tandem Lewis basic Ir and Lewis acidic P of achieve a two-site oxidative addition of phenol giving the iridaphenoxyphosphorane species IrHCl(PPh)() (). In contrast, reactions of with benzenethiol and benzeneselenol do not engage and instead proceed via metal-centered oxidative addition of the chalcogen-hydrogen bond. These findings establish metal-ligand cooperation involving nonspectator reactivity of tricoordinate phosphorus ligands.