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

ABSTRACT

The synthesis and reactivity of an ambiphilic iridium complex IrCl(PPh3)(L1) (1; L1 = P(N(o-N(2-pyridyl)C6H4)2)) featuring a chelating nontrigonal phosphorus triamide ligand is reported. The tandem Lewis basic Ir and Lewis acidic P of 1 achieve a two-site oxidative addition of phenol giving the iridaphenoxyphosphorane species IrHCl(PPh3)(L1OPh) (3'). In contrast, reactions of 1 with benzenethiol and benzeneselenol do not engage L1 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.