Mechanism and energetics of reductive elimination of ethane from some tetramethylplatinum(IV) complexes

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Abstract

The new complexes cis-[PtMe4L2], L = MeNC or 2,6-Me2C6H3NC, decompose cleanly in the solid state or in solution to give ethane and cis-[PtMe2L2]. Studies using differential scanning calorimetry give a value of (PtMe)= 133 ± kJ mol–1for the mutually trans PtMe groups, and deuterium-labelling studies show that the reductive elimination step is intramolecular. Kinetic studies show that the reaction occures very largely after ligand dissociation and gives a value of k(PtCH3)/k(PtCD3)= 1.30 ± 0.04. It is suggested that an agostic interaction of one CH3Pt group in the five-co-ordinate intermediate precedes the reductive elimination step and reasons for this proposal are advanced.

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