Abstract
The rates of reactions of methyl iodide with four-coordinated iridium(I) complexes, [rL 2XY with X = Cl, and Y = CO, generally increase with increasing basicity of L such as P(OPh) 3<PPh 3<P( p-tolyl) 3<PMePh 2<PEt 3<PMe 2Ph. Triphenylarsine iridium(I) complexes react faster with methyl iodide than the corresponding triphenylphosphine complexes. The rates for the iridium complexes with L 2 and X = Cl increase as Y is CO<PPh 3<N 2. The rates for the complexes with Y = CO and L = PPH 3, AsPh, P( p-tolyl) 3, or PMe 2Ph increase as X is I<Br<Cl, and reasons for the increasing rates with decreasing basicity or decreasing tendency of the iridium complex to undergo oxidative addition upon variation of X have been suggested. The rates for the complexes with X = CO and L = PPh 3 and AsPh 3 increase as X is NCS<NCO<NNN. The dependence of the rates on L and X are compared with data for reactions of iridium(I) complexes with oxygen and hydrogen, and mechanistic implications are discussed.
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