Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 122, Issue 3, Pages 1278-1288Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.7b12093
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Funding
- National Science Foundation
- NSF [CHE-1214131, CBET-1433521, CHE-1112564, ACI-1053575]
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1433521] Funding Source: National Science Foundation
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We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy Delta G(double dagger) of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute Delta G(double dagger) for hydride transfers from hydride donors to CO2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted Delta G(double dagger); this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled. rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.
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