Mechanistic Investigation of Biocatalytic Heme Carbenoid Si-H Insertions.

ABSTRACT: Recent studies reported the development of biocatalytic heme carbenoid Si-H insertions for the selective formation of carbon-silicon bonds, but many mechanistic questions remain unaddressed. To this end, a DFT mechanistic investigation was performed which reveals an Fe^II-based concerted hydride transfer mechanism with early transition state feature. The results from these computational analyses are consistent with experimental data of radical trapping, kinetic isotope effects, and structure-reactivity data using engineered variants of hemoproteins. Detailed geometric and electronic profiles along the heme catalyzed Si-H insertion pathways were provided to help understand the origin of experimental reactivity trends. Quantitative relationships between reaction barriers and some p

SUBMITTER: Khade RL 

PROVIDER: S-EPMC6699785 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature