Structural and Thermodynamic Effects on the Kinetics of C-H Oxidation by Multisite Proton-Coupled Electron Transfer in Fluorenyl Benzoates.

ABSTRACT: Our recent experimental and theoretical investigations have shown that fluorene C-H bonds can be activated through a mechanism in which the proton and electron are transferred from the C-H bond to a separate base and oxidant in a concerted, elementary step. This multisite proton-coupled electron transfer (MS-PCET) mechanism for C-H bond activation was shown to be facilitated by shorter proton donor-acceptor distances. With the goal of intentionally modulating this donor-acceptor distance, we have now studied C-H MS-PCET in the 3-methyl-substituted fluorenyl benzoate (2-Flr-3-Me-BzO^-). This derivative was readily oxidized by ferrocenium oxidants by initial C-H MS-PCET, with rate constants that were 6-21 times larger than those for 2-Flr-BzO^- with the same oxidants. Str

SUBMITTER: Koronkiewicz B 

PROVIDER: S-EPMC9167551 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature