title: A Frustrated Phosphane-Borane Lewis Pair and Hydrogen: A Kinetics Study.
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.
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149, Münster, Corrensstrasse 40, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Özgün
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149, Münster, Corrensstrasse 40, Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Bergander
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, 53115, Bonn, Beringstrasse 4, Germany.
authors.forename: Lei
authors.initials: L
authors.lastname: Liu
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149, Münster, Corrensstrasse 40, Germany.
authors.forename: Constantin G
authors.initials: CG
authors.lastname: Daniliuc
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, 53115, Bonn, Beringstrasse 4, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149, Münster, Corrensstrasse 40, Germany.
authors.forename: Gerald
authors.initials: G
authors.lastname: Kehr
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149, Münster, Corrensstrasse 40, Germany. erker@uni-muenster.de.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Erker
keywords: density dunctional calculations; deuterium isotope effect; frustrated Lewis pairs; hydrogen splitting; kinetics; phosphane-boranes