Majid Hashemi

The reactivities of Pt(II) center in a series of organometallic mononuclear Pt(II), binuclear Pt(II) and binuclear mixed-valence Pt(II)ePt(IV) complexes toward oxidative addition of MeI have been compared from a theoretical point of view. The nucleophilicity index and electron-donation power were calculated for each of these complexes. The energies of HOMO and dZ2 orbital were determined for these complexes. Very good correlations were found between logk2 (k2 is the experimentally determined second order rate constant for the oxidative addition of MeI on these complexes) and nucleophilicity index or electron-donation power for these complexes. The correlation between logk2 and the energy of HOMO or the energy of dZ2 orbital were also very good. The condensed-to-atom Fukui functions for electrophilic attack on these complexes showed that the Pt(II) center is the preferred site for the oxidative addition of MeI. All of these observations are in agreement with the proposed SN2 type mechanism in the oxidative addition of MeI on the Pt(II) center in these complexes.