Open AccessTemperature-Dependent Reactivity of a Non-heme FeIII(OH)(SR) Complex: Relevance to Isopenicillin N Synthase
Author(s) -
Vishal Yadav,
Maxime A. Siegler,
David Goldberg
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c09688
Subject(s) - chemistry , reactivity (psychology) , heme , selectivity , sulfur , stereochemistry , heme oxygenase , oxygen , atp synthase , enzyme , catalysis , organic chemistry , medicine , alternative medicine , pathology
Non-heme iron complexes with cis -Fe III (OH)(SAr/OAr) coordination were isolated and examined for their reactivity with a tertiary carbon radical. The sulfur-ligated complex shows a temperature dependence on • OH versus ArS • transfer, whereas the oxygen-ligated complex does not. These results provide the first working model for C-S bond formation in isopenicillin N synthase and indicate that kinetic control may be a key factor in the selectivity of non-heme iron "rebound" processes.