BOND ENERGIES AND THERMAL DECOMPOSITION OF 2> COMPLEXES

Article abstract of DOI:10.1016/0022-328X(83)80227-7

The thermal decomposition of the complexes trans- (L = P(C2H5)3; X = Cl, Br, I, CN) in decalin at 170 and 200 deg affords methane, platinum metal and .The kinetics of the decomposition of the complexes were determined by monitoring the appearance of methane by GLC.The observed first-order rate constant was found to be independent on the nature of the ligand X.The thermal decomposition of the trideuteriomethyl complexes (X = I, CN) in decalin-d₁₈ at 170 and 200 deg C was studied by GLC/MS.The thermolysis affords CD3H and CD4 in ratios which are independent of the nature of X and of the temperature used.The mass spectra of the complexes were also examined.A relative scale of platinum-to-methyl bond dissociation energies has been established by measuring the appearance potential of the fragment ion ⁺ and the ionization energies in the series .Ionization potentials and Pt-CH3 bond energies show a clear dependence on the nature of X which is not reflected in corresponding changes in the decomposition rates.