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Comparison of Intramolecular and Intermolecular Ammonium and Phosphonium Borohydrides in Hydrogen‐, Proton‐, and Hydride‐Transfer Reactions
Author(s) -
Lathem A. Paige,
Rinne Benjamin L.,
Maldonado Marc A.,
Heiden Zachariah M.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700016
Subject(s) - intramolecular force , chemistry , phosphonium , hydride , borohydride , intermolecular force , phosphine , medicinal chemistry , photochemistry , catalysis , organic chemistry , hydrogen , molecule
In this computational study, the thermodynamics of H 2 , proton, and hydride transfer from 13 ammonium borohydride and six phosphonium borohydride intramolecular and intermolecular frustrated Lewis pairs (FLPs) was probed to gain insight into whether intramolecular or intermolecular amine‐containing FLPs are preferred to phosphine‐containing FLPs in FLP‐catalyzed hydrogenation reactions. H 2 , hydride, and proton transfer from intramolecular ammonium borohydrides was, on average, 2.6 kcal/mol, 0.7 kcal/mol, and about 3.8 p K a units, respectively, less likely than from intramolecular phosphonium borohydrides. Using the thermodynamic quantities for H 2 , hydride, and proton transfer to eight probe substrates, intramolecular phosphonium borohydrides were found to be thermodynamically preferred to intramolecular ammonium borohydrides in catalytic hydrogenation reactions.