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A Frustrated Phosphane–Borane Lewis Pair and Hydrogen: A Kinetics Study
Author(s) -
Özgün Thomas,
Bergander Klaus,
Liu Lei,
Daniliuc Constantin G.,
Grimme Stefan,
Kehr Gerald,
Erker Gerhard
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603050
Subject(s) - frustrated lewis pair , borane , endothermic process , chemistry , kinetics , kinetic energy , kinetic isotope effect , hydrogen , reaction rate constant , computational chemistry , activation energy , cleavage (geology) , lewis acids and bases , organic chemistry , catalysis , deuterium , materials science , atomic physics , physics , adsorption , quantum mechanics , fracture (geology) , composite material
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 H 2 ‐cleavage product by sequential H + /H − addition. The system could be handled at low temperature, and the kinetics of the H 2 elimination were determined to give a rate constant of k HH,exp (299 K)=(2.87±0.1)×10 −4 s −1 in solution. The primary kinetic isotope effects were determined; for example, ( k HH / k DD ) exp =3.19. The system was accurately analyzed by DFT calculations.