The interaction between cysteine and nonheme Fe(III) has received considerable attention given the ubiquity of both in life processes. Early observations, spanning back multiple decades, were made using non-chelated Fe(III) leading to complications in spectral analyses. These complications originate from the presence of up to three cysteine equivalents per metal center, and the need for a relatively acidic or alkaline solution to prevent precipitation of Fe(III) aqua ion. Herein we describe the use of the neutral, tridentate ligand triazacyclononane to restrict open coordination sites on Fe(III) for cysteine binding and also to enable studies in neutral, buffered solutions. The results described suggest significant differences in Fe(III)-thiolate reactivity as a function of cysteine binding mode.

Delineating the effect of cysteine binding mode on Fe(III)-thiolate homocoupling rate

ACS Spring 2022

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