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Temperature-Dependent Reactivity of a Non-heme FeIII(OH)(SR) Complex: Relevance to Isopenicillin N Synthase.

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Non-heme iron complexes with cis-FeIII(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,… Click to show full abstract

Non-heme iron complexes with cis-FeIII(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.

Keywords: temperature; heme; reactivity; isopenicillin synthase; non heme

Journal Title: Journal of the American Chemical Society
Year Published: 2020

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