Kinetic investigations of the Oxidative Addition Reactions of Simple Molecules with Carbon-Carbon Multiple Bonds to {Ir(CO)XL2}-type complexes

The kinetics of the addition reactions of tetracyanoethylene (TCNE), dimethyl maleate (DMM), diethyl maleate (DEM), maleicanhydride (MA), acetylenedicarboxylic acid (ADCA) and dimethyl acetylenedicarboxylate (DMADC) to complexes of the type trans-{Ir(CO)XL₂} (X = Cl, Br, I; L = P(C₆H₅)₃, P(p-CH₃C₆H₄)₃, P(p-CH₃OC₆H₄)₃, P(OC₆H₅)₃) in various solvents were investigated employing stopped-flow techniques. The kinetics were found to obey a second order/first order rate law for a reversible process. The rate constants obtained are discussed in terms of a Lewis acid-base model.