Reversible oxygenation of metal complexes: electronic and steric factors

Abstract

The rates of oxygen addition to trans-[IrCl(CO)-(R3P)2](R3P = tertiary phosphine) and the stability of the resulting dioxygen adducts, [O2IrCl(CO)(R3P)2], increase with increasing basicity of the substituent R, provided the substituents have comparable structures; the geometry of R exerts a profound effect on the dynamics of these reactions.