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Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics
Author(s) -
Burgess Samantha A.,
Appel Aaron M.,
Linehan John C.,
Wiedner Eric S.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709319
Subject(s) - catalysis , chemistry , formate , solvent , hydride , reagent , tetrahydrofuran , thermodynamics , organic chemistry , hydrogen , physics
A critical scientific challenge for utilization of CO 2 is the development of catalyst systems that function in water and use inexpensive and environmentally friendly reagents. We have used thermodynamic insights to predict and demonstrate that the HCo I (dmpe) 2 catalyst system, previously described for use in organic solvents, can hydrogenate CO 2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO 2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water owing to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity.