Ab Initio Molecular Dynamics with Explicit Solvent Reveals a Two‐Step Pathway in the Frustrated Lewis Pair Reaction |
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| Authors: | Maoping Pu Prof. Dr. Timofei Privalov |
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| Affiliation: | Stockholm University, Department of Organic Chemistry, Arrhenius Laboratory, Stockholm 10691 (Sweden) |
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| Abstract: | 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 CO2 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 P?C and O?B bonds—is that the environment (typical organic solvents) stabilizes an intermediate which results from nucleophilic attack of the phosphorus Lewis base on CO2. 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. |
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| Keywords: | Lewis acid Lewis bases molecular modeling reaction mechanisms reactive intermediates |
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