A Frustrated Phosphane–Borane Lewis Pair and Hydrogen: A Kinetics Study |
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| Authors: | Thomas Özgün Dr. Klaus Bergander Dr. Lei Liu Dr. Constantin G. Daniliuc Prof. Dr. Stefan Grimme Dr. Gerald Kehr Prof. Dr. Gerhard Erker |
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| Affiliation: | 1. Organisch-Chemisches Institut, Westf?lische Wilhelms-Universit?t, Münster, Germany;2. Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universit?t Bonn, Bonn, Germany |
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| Abstract: | The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene‐bridged phosphane–borane FLP was converted into its endothermic H2‐cleavage product by sequential H+/H? addition. The system could be handled at low temperature, and the kinetics of the H2 elimination were determined to give a rate constant of kHH,exp(299 K)=(2.87±0.1)×10?4 s?1 in solution. The primary kinetic isotope effects were determined; for example, (kHH/kDD)exp=3.19. The system was accurately analyzed by DFT calculations. |
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| Keywords: | density dunctional calculations deuterium isotope effect frustrated Lewis pairs hydrogen splitting kinetics phosphane– boranes |
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