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Quantum Chemical Analyses of BH 4 − and BH 3 OH − Hydride Transfers to CO 2 in Aqueous Solution with Potentials of Mean Force
Author(s) -
Groenenboom Mitchell C.,
Keith John A.
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201700608
Subject(s) - hydride , solvation , aqueous solution , chemistry , borohydride , potential of mean force , sodium borohydride , umbrella sampling , computational chemistry , molecule , molecular dynamics , catalysis , hydrogen , organic chemistry
Biomimetic hydride transfer catalysts are a promising route to efficiently convert CO 2 into more useful products, but a lack of understanding about their atomic‐scale reaction mechanisms slows their development. To this end, we report a computational quantum chemistry study of how aqueous solvation influences CO 2 reduction reactions facilitated by sodium borohydride (NaBH 4 ) and a partially oxidized derivative (NaBH 3 OH). This work compares 0 K reaction barriers from nudged elastic band calculations to free‐energy barriers obtained at 300 K using potentials of mean force from umbrella sampling simulations. We show that explicitly treating free energies from reaction pathway sampling has anywhere from a small to a large effect on the reaction‐energy profiles for aqueous‐phase hydride transfers to CO 2 . Sampling along predefined reaction coordinates is thus recommended when it is computationally feasible.