Abstract

High-valent transition metal-oxo complexes exhibit a wide range of reactivities and play essential roles as active Oxygen Atom Transfer (OAT) species in many chemical and biological oxidation processes. However, the detection and characterization of these intermediates are still challenging in view of their high reactivity and short lifetimes and their transient nature makes their study complex. This review highlights recent advancements in how photochemical reactions with visible light have emerged as promising approaches to generate and study high-valent transition metal-oxo species with different metals on various macrocyclic ligands. Investigating the reactivity of photo-induced high-valent metal-oxo species through practical kinetic studies has offered valuable insights into the structure-function relationships and an understanding of their involvement in oxidation reactions.

Keywords:Metal-oxo derivatives; Porphyrin; Corrole; Salen; Phthalocyanine, Oxidation; Visible light photolysis; Kinetics

Abbreviations:ESI-MS: Electron Spray Ionization-Mass Spectrometry; ET: Electron Transfer; LFP: Laser Flash Photolysis; OAT: Oxygen Atom Transfer; Por: Porphyrin; Sub-O: Substrate oxidized product; Salen N: N’-bis(salicylidene)ethylenediamine; tBu4-Pc: Tetra-tert-butyl-phthalocyanine; TDCPP: 5,10,15,20-tetra(2,6-dichlorophenyl) porphyrin; TDFPP: 5,10,15,20-tetra(2,6-difluorophenyl) porphyrin; TMP: Tetramesitylporphyrin; TPP: Tetraphenylporphyrin; TPFPP: 5,10,15,20-tetra(pentafluorphenyl) porphyrin; TPC: 5,10,15-triphenylcorrole; TPFC: 5,10,15-tripentafluorophenylcorrole.