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Generation of σ-Aryl Platinum(IV) Complexes in Mechanically Activated Reaction of K2PtCl6 with Arenes

Research paper by A. A. Shubin, S. A. Mitchenko, E. V. Khomutov, V. V. Kovalenko, I. P. Beletskaya

Indexed on: 01 Mar '04Published on: 01 Mar '04Published in: Russian Journal of Organic Chemistry



Abstract

Mechanical activation of K2PtCl6 in the presence of gaseous arenes RH (where R = Ph, MeC6H4) gives rise to the corresponding σ-aryl platinum(IV) complexes, whose formation is confirmed by the 1H NMR and IR spectra and chemical testing. The reaction with toluene gives a statistical mixture of the corresponding meta- (66%) and para-isomeric complexes (33%) with an overall energy yield of 0.08 µmol/J. According to the results of ab initio calculations, the energies of the isomers are fairly similar; therefore, their formation is equally probable from the viewpoint of thermodynamics.