Combined Multistate and Kohn-Sham Density Functional Theory Studies of the Elusive Mechanism of N-Dealkylation of N,N-Dimethylanilines Mediated by the Biomimetic Nonheme Oxidant Fe^IV(O)(N4Py)(ClO₄)₂.

ABSTRACT: The oxidative C-H bond activation mediated by heme and nonheme enzymes and related biomimetics is one of the most interesting processes in bioinorganic and oxidative chemistry. However, the mechanisms of these reactions are still elusive and controversy due to the involvement of highly reactive metal-oxo intermediates with multiple spin states, despite extensive experimental efforts, especially for the N-dealkylation of N,N-dialkyalinines. In this work, we employed multistate density functional theory (MSDFT) and the Kohn-Sham DFT to investigate the mechanism of N-demethylation of N,N-dimethyalinines oxidized by the reaction intermediate Fe^IV(O)(N4Py)(ClO₄)₂. The Kohn-Sham DFT study demonstrated that the reaction proceeds via a rate-limiting hydrogen atom t

SUBMITTER: Yang L 

PROVIDER: S-EPMC6139341 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature