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On the Mechanism of Irreversible Carbon Dioxide Binding with a Frustrated Lewis Pair: Solvent‐Assisted Frustration and Transition‐State Entropic Encouragement
Author(s) -
Kwon Hee Jae,
Kim Hyun Woo,
Rhee Young Min
Publication year - 2011
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.201003483
Subject(s) - steric effects , chemistry , frustrated lewis pair , solvation , solvent , lewis acids and bases , frustration , adduct , computational chemistry , molecule , chemical physics , stereochemistry , organic chemistry , catalysis , neuroscience , biology
The mechanism of irreversible carbon dioxide binding with a Lewis pair Mes 3 P:AlCl 3 (Mes=2,4,6‐C 6 H 2 Me 3 ) is computationally investigated to reveal that the steric congestion is not the driving force for the activation of CO 2 . Instead, we find that the specific solute–solvent interaction between the Lewis acid and a bromobenzene molecule lowers the effective binding energy of the Lewis pair. This solvation effect affects the reaction in a similar manner to the steric encumbering of conventional frustrated Lewis pairs. Additionally, the transition state toward the CO 2 binding becomes extraordinarily flexible upon solvation. This flexibility encourages the adduct formation entropically and thus lowers the free‐energy barrier of the reaction. We conclude that this combination of energy‐barrier lowering through solvent‐assisted frustration and the entropic encouragement generates a feasible activation route for CO 2 under mild conditions.