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

Inorganic Chemistry
Bror Johan WikRudi van Eldik

Abstract

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 DeltaH = 15.2 +/- 0.6 kJ mol(-1) and DeltaS = -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 DeltaH = 75 +/- 1 kJ mol(-1), DeltaS = +38 +/- 5 J mol(-1) K(-1), and DeltaV = +18 +/- 1 cm(3) mol(-1), strongly suggesting a dissociative character of the rate-determining step for the reductive elimination reacti...Continue Reading

References

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Jun 9, 2005·Chemical Reviews·Martin Lersch, Mats Tilset

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Citations

Sep 24, 2011·Inorganic Chemistry·Gloria MazzoneEmilia Sicilia
Mar 19, 2016·Chemistry : a European Journal·Jesús CamposErnesto Carmona
May 12, 2015·Chemistry : a European Journal·Jesús CamposErnesto Carmona
Jun 6, 2009·Journal of the American Chemical Society·Wesley H BernskoetterMaurice Brookhart
Apr 1, 2009·Journal of the American Chemical Society·Marc-Etienne Moret, Peter Chen

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