Calorimetric Study of the Activation of Hydrogen by Tris(pentafluorophenyl)borane and Trimesitylphosphine

The Journal of Physical Chemistry. a
Adrian Y Houghton, Tom Autrey

Abstract

The mechanism of H2heterolysis by the frustrated Lewis pair of B(C6F5)3and P(mes)3was investigated by isothermal reaction calorimetry in the temperature range from 30 to 90 °C. The experimental heat curves were modeled in Berkeley Madonna to obtain both kinetic and thermodynamics data simultaneously. The H2activation reaction is treated as a single, termolecular step with a rate constant of 0.61 M-2s-1at 303 K with an exothermic enthalpy of reaction, ΔHH2= -141 kJ/mol. An Eyring analysis gave activation parameters of ΔH‡= 13.6(9) kJ mol-1and ΔS‡= -204(85) J K-1mol-1. Using D2gas in place of H2gas provided an opportunity to measure the relative rates of D2versus H2heterolysis to yield a the kinetic isotope effect, KIE = 1.1(1).

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Citations

Apr 11, 2019·Angewandte Chemie·Elliot L BennettJ Chris Slootweg
Mar 10, 2020·Chemistry : a European Journal·Ryan Andrews, Douglas Wade Stephan
Jan 11, 2019·Chemical Science·Roland C Turnell-RitsonAndrew E Ashley
Mar 4, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Mojgan Heshmat
Oct 2, 2020·Inorganic Chemistry·Mark E BowdenTom Autrey

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