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Frontier Molecular Orbital Contributions to Chlorination versus Hydroxylation Selectivity in the Non-Heme Iron Halogenase SyrB2
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SYSNO ASEP 0471846 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Frontier Molecular Orbital Contributions to Chlorination versus Hydroxylation Selectivity in the Non-Heme Iron Halogenase SyrB2 Author(s) Srnec, Martin (UFCH-W) RID, ORCID
Solomon, E. I. (US)Source Title Journal of the American Chemical Society. - : American Chemical Society - ISSN 0002-7863
Roč. 139, č. 6 (2017), s. 2396-2407Number of pages 12 s. Language eng - English Country US - United States Keywords Chlorination ; Chlorine compounds ; Free radical reactions Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GJ15-10279Y GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000394482200042 EID SCOPUS 85013059462 DOI 10.1021/jacs.6b11995 Annotation The ability of an Fe-IV=O intermediate in SyrB2 to perform chlorination versus hydroxylation was computationally evaluated for different substrates that had been Studied experimentally. The pi-trajectory for H atom abstraction (Fe-IV=O oriented perpendicular to the C-H bond of substrate) was found to lead to the S = 2 five-coordinate HO-Fe-III-Cl complex with the C-center dot of the substrate, pi-oriented relative to both the Cl- and the OH- ligands. From this ferric intermediate, hydroxylation is thermodynamically faVored, but chlorination is intrinsically more reactive due to the energy splitting between two key redox-active d pi* frontier Molecular orbitals (FMOs). The splitting is determined by the differential ligand field effect of Cl- OH- versus on the Fe center. This makes chlorination effectively competitive with hydroxylation. Chlorination versus hydroxylation selectivity is then determined by the orientation of the substrate with respect to the HO-Fe-Cl plane that controls either the Cl- or the OH- to rebound depending on the relative pi-overlap with the substrate C radical. The differential contribution of the two FMOs to chlorination versus hydroxylation selectivity in SyrB2 is related to reaction mechanism that involves two asynchronous transfers: electron transfer from the substrate radical to the iron center followed by late ligand (Cl- or OH-) transfer to the substrate. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2018
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