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Room Temperature Alkali Metal Reduction of Carbon Dioxide

preprint
revised on 04.08.2020 and posted on 05.08.2020 by Lucas A. Freeman, Akachukwu D. Obi, Haleigh R. Machost, Andrew Molino, Asa W. Nichols, Diane A. Dickie, David J. D. Wilson, Charles Machan, Robert Gilliard
The reduction of the relatively inert carbon–oxygen bonds of CO2 to access useful CO2-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO2 and the MGE. Herein we report the first successful chemical reduction of CO2 at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO2)]n(M = Li, Na, K, 2-4) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M2(CAAC–CO2)]n (5-8). It is notable that these crystalline clusters of reduced CO2 may also be isolated via the “one-pot” reaction of free CO2 with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products 2-8 were investigated using a combination of experimental and theoretical methods.

Funding

University of Virginia, Latrobe University

History

Email Address of Submitting Author

rjg8s@virginia.edu

Institution

University of Virginia

Country

United States

ORCID For Submitting Author

0000-0002-8830-1064

Declaration of Conflict of Interest

No Conflicts

Exports