Studies of Iron Complexes with Tridentate Bis(thiolato)phosphine Ligands

Abstract

Iron thiolate chemistry has been an interesting research area due to its relevance in biological systems such as cytochrome P450 (CYPs) and cysteine dioxygenase (CDO) To understand the fundamental iron thiolate chemistry our lab has utilized (thiolato)phosphine ligand derivatives to explore iron chemistry At this wok we report three iron complexes binding with two bis(benzenethiolate)phosphine derivatives PS2” and PS2 (PS2” = [P(C6H5)(C6H3-3-Me3Si-2-S)2]2- and PS2’ = [P(C6H5)(C6H3-4-Me-2-S)2]2-) Three complexes [FeIII(PS2”)2]- (1) [FeIII(PS2’)2]- (2) and [Fe(PS2”)2] (3) are well characterized and studied by X-ray crystallography elemental analysis various spectroscopies and physical methods Based on various spectroscopic and magnetic data complex 3 likely has an electronic structure of [FeIII(PS2”)(PS2”‧)] where PS2”‧ is PS2” ligand with a thiyl radical character The redox chemistry of these complexes are further investigated In addition complexes 1 and 2 are air-stable in contrast complex 3 reacts with dioxygen to generate ligand-based oxygenation products such as phosphine-oxide or sulfinate containing complexes The reactions are monitored by ESI-MS combined with isotope studies

Date of Award	2020
Original language	English
Supervisor	Hua-Fen Hsu (Supervisor)