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Ensemble Effects of Explicit Solvation on Allylic Oxidation

preprint
submitted on 19.01.2021, 20:32 and posted on 22.01.2021, 07:21 by Hung Le, Mariano Guagliardo, Anne Gorden, Aurora Clark
Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene
using a Cu(II) (E)-6-amino-7-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile, which creates the desired cyclohexenone and H 2 O as products. In comparison to prior study using gas-phase DFT, a significant solvent effect is observed on the rate determining allylic H-atom abstraction step (which has a free energy barrier of 12.1 ± 0.2 kcal/mol). During the cycle, the explicit solvation and ensemble sampling of solvent configurations reveals an important dehydrogenation and re-hydrogenation step of the -NH 2 ligand that is essential to catalyst recovery. This work illustrates the importance of ensemble solvent configurational sampling to reveal the breadth of processes that underpin the full catalytic cycle.

History

Email Address of Submitting Author

hung.le2@wsu.edu

Institution

Washington State University

Country

USA

ORCID For Submitting Author

0000-0002-1276-9584

Declaration of Conflict of Interest

There is no conflict of interest to declare.

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