Role of oxidation state, ferryl-oxygen, and ligand architecture on the reactivity of popular high-valent FeIV=O species: A theoretical perspective

摘要: Abstract High-valent iron-oxo species are ubiquitous in nature and present at the active site of several metalloenzymes which perform challenging organic transformations. Mimicking these metalloenzyme reactivities is one growing areas research, over last two decades, tremendous progress has been made to mimic both structure function various heme non-heme metalloenzymes. Understanding mechanism catalytic reactions enzymes their biomimetic models extremely important improvise further. However, due open-shell catalyst with often close-lying spin-states, mechanistic aspects associated highly complex. In this regard, computational tools have played a pivotal role underpinning concepts such as two-state/multi-state reactivity, exchange-enhanced reactivity emerged. While there reviews written already on popular high-valent FeIV=O species, comparative oxidative ability other oxidants not reviewed. Our group working actively area, here we compared variation arising (i) oxidation state (ii) ligand architecture (iii) substitution oxo by isoelectronic nitrene species. review, theoretical studies undertaken spirit summarised provide birds-eye-view The facts/concepts discussed will undoubtedly be helpful design efficient bioinspired catalysts years come.