Metallopeptide-based mimics suggest substrate orientation directs sulphur oxidation vs. hydrogen atom abstraction reactions in mononuclear non-haem iron dioxygenases

Abstract

Active metallopeptide based mimics of substrate-bound cysteine dioxygenase (CDO) and isopenicillin-N-synthase (IPNS) suggest that differential reactivity between the two metalloenzymes results from the orientation of a chemically active S(3p_π) dominated MO relative to the Fe(III)–O₂⁻ moiety.