Iodo-methyl ligand exchange reaction in platinum complexes: A density functional study

A theoretical investigation at the gradient-corrected density functional (BP86) level of theory on the iodo-methyl ligand exchange reaction in platinum–diphosphine complexes is discussed. The reaction consists of two elementary steps: the oxidative addition of methyl–iodide, and reductive elimination of ethane from the intermediate Pt(bdpp)(CH3)3I complex which is the rate determining step with a free energy of activation of 19.5 kcal/mol in acetonitrile phase. The oxidative addition step takes place with SN2 mechanism via a transition state with a collinear arrangement of the I–CH3–Pt moiety.