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Ab Initio Molecular Dynamics with Explicit Solvent Reveals a Two‐Step Pathway in the Frustrated Lewis Pair Reaction
Author(s) -
Pu Maoping,
Privalov Timofei
Publication year - 2015
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.201502926
Subject(s) - frustrated lewis pair , lewis acids and bases , chemistry , nucleophile , computational chemistry , molecular dynamics , concerted reaction , solvent , transition state , reaction mechanism , reactivity (psychology) , ab initio , catalysis , organic chemistry , medicine , alternative medicine , pathology
The role solvent plays in reactions involving frustrated Lewis pairs (FLPs)—for example, the stoichiometric mixture of a bulky Lewis acid and a bulky Lewis base—still remains largely unexplored at the molecular level. For a reaction of the phosphorus/boron FLP and dissolved CO 2 gas, first principles (Born–Oppenheimer) molecular dynamics with explicit solvent reveals a hitherto unknown two‐step reaction pathway—one that complements the concerted (one‐step) mechanism known from the minimum‐energy‐path calculations. The rationalization of the discovered reaction pathway—that is, the stepwise formation of PC and OB bonds—is that the environment (typical organic solvents) stabilizes an intermediate which results from nucleophilic attack of the phosphorus Lewis base on CO 2 . This finding is significant because presently the concerted reaction‐path paradigm predominates in the rationalization of FLP reactivity. Herein we point out how to attain experimental proof of our results.