Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 49, Pages 17708-17720Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502926
Keywords
Lewis acid; Lewis bases; molecular modeling; reaction mechanisms; reactive intermediates
Categories
Funding
- Berzelius Center EXSELENT
- Knut and Alice Wallenberg foundation
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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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