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Abstract
In addition to its primary oxygen-atom-transfer function, cysteamine dioxygenase (ADO) exhibits an understudied disproportionation reaction (ADO-Fe(III)-SR → ADO-Fe(II) + ½ RSSR) with its native substrates. Inspired by ADO disproportionation reactivity, we employ [Fe(tacn)Cl3] (tacn = 1,4,7-triazacyclononane) as a precursor for generating Fe(III)–thiolate intermediates in buffered aqueous media. A series of Fe(III)–thiolate intermediates are generated in situ using aqueous [Fe(tacn)Cl3] and thiol-containing ligands cysteamine, penicillamine, mercaptopropionate, cysteine, cysteine methyl ester, N-acetylcysteine, and N-acetylcysteine methyl ester. We observe trends in UV–vis and electron paramagnetic resonance (EPR) spectra, disproportionation rate constants, and cathodic peak potentials as a function of thiol ligand. These trends will be useful in rationalizing substrate-dependent Fe(III)–thiolate disproportionation reactions in metalloenzymes.
Supplementary materials
Title
Supporting Information
Description
UV-vis spectra of 1(aq) + cysteine methyl ester, NMR spectra of cysteine to cystine conversion, Mass spectra demonstrating disulfide formation, EPR spectra, FT-IR spectrum of 2, NMR spectra of 2.
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