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Mechanism and Chemoselectivity for HOCl‐Mediated Oxidation of Zinc‐Bound Thiolates
Author(s) -
Zumwalt Lindsay,
Perkins Arden,
Ogba O. Maduka
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000634
Subject(s) - chemoselectivity , chemistry , zinc , redox , nucleophile , mechanism (biology) , hypochlorous acid , reaction mechanism , combinatorial chemistry , limiting , photochemistry , organic chemistry , catalysis , philosophy , epistemology , mechanical engineering , engineering
Quantum mechanical calculations reveal the preferred mechanism and origins of chemoselectivity for HOCl‐mediated oxidation of zinc‐bound thiolates implicated in bacterial redox sensing. Distortion/interaction models show that minimizing geometric distortion at the zinc complex during the rate‐limiting nucleophilic substitution step controls the mechanistic preference for OH over Cl transfer with HOCl and the chemoselectivity for HOCl over H 2 O 2 .