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An Iron(lV)-oxo heme(+·) complex (Compound I, Cpd I) is the proposed active species of heme enzymes such as the cytochromes P450 and Is elusive; therefore, biomimetic studies on active site mimics give valuable Insight Into the fundamental properties of heme active species. In this work we present density functional theory (DFT) calculations on substrate hydroxylatlon by a Compound I mimic [FeIV=O(Por+̇)Cl] and its one-electron reduced form [FeIV=O(Por)Cl]-. Thus, recent experimental studies showed that [FeIV =O(Por)Cl]- is able to react with substrates via hydride transfer reactions [Jeong, Y. J.; Kang, Y.; Han, A.-R.; Lee, Y.-M.; Kotani, H.; Fukuzumi, S.; Nam, W. Angew. Chem., Int. Ed.... 

Combined experimental and theoretical studies on the reactivity of iodosylbenzene (PhIO) show that PhIO is capable of activating weak C-H bonds of hydrocarbons via a hydrogen abstraction mechanism. © 2009 The Royal Society of Chemistry  

In this work we present results of density functional theory (DFT) calculations on dicopper patellamides and their affinity for molecular oxygen and carbonate. Patellamides are cyclic octapeptides that are produced by a cyanobacterium, and may show promise as therapeutics. Thus, carbonate binding to a dicopper patellamide center gives a stable cyclic octapeptide with a twist of almost 90°. The system exists in close-lying open-shell singlet and triplet spin states with two unpaired electrons in orthogonal σ* orbitals on each metal center. Subsequently, we replaced carbonate with dioxygen and found a stable Cu2(μ-O)2 diamond shaped patellamide core. In this structure the original dioxygen...