Inorganic Chemistry, Vol.45, No.9, 3613-3621, 2006
Mechanistic information from low-temperature rapid-scan and NMR measurements on the protonation and subsequent reductive elimination reaction of a (diimine)platinum(II) dimethyl complex
A detailed kinetic study of the protonation and subsequent reductive elimination reaction of a (diimine)platinum(II) dimethyl complex was undertaken in dichloromethane over the temperature range of -90 to +10 degrees C by stopped-flow techniques. Time-resolved UV-vis monitoring of the reaction allowed the assessment of the effects of acid concentration, coordinating solvent (MeCN) concentration, temperature, and pressure. The second-order rate constant for the protonation step was determined to be 15200 400 M-1 s(-1) at -78 degrees C, and the corresponding activation parameters are Delta H-double dagger = 15.2 +/- 0.6 U mol(-1) and Delta S-double dagger = -85 +/- 3 J mol(-1) K-1, which are in agreement with the addition of a proton that results in the formation of the platinum(IV) hydrido complex. The kinetics of the second, methane-releasing reaction step do not show an acid dependence, and the MeCN concentration also does not significantly affect the reaction rate. The activation parameters for the second reaction step were found to be Delta H-double dagger = 75 1 U mol-1, Delta S-double dagger = +38 +/- 5 J mol(-1) K-1, and Delta V-double dagger = +18 +/- 1 cm(3) Mol(-1), strongly suggesting a dissociative character of the rate-determining step for the reductive elimination reaction. The spectroscopic and kinetic observations were correlated with NMR data and assisted the elucidation of the underlying reaction mechanism.