Mechanism and energetics of reductive elimination of ethane from some tetramethylplatinum(IV) complexes
- 1 January 1989
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 11,p. 2121-2125
- https://doi.org/10.1039/dt9890002121
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.Keywords
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