Reaction Mechanisms of Metalloenzymes and Synthetic Model Complexes Activating Dioxygen Reaction Mechanisms of Metalloenzymes and Synthetic Model Complexes Activating Dioxygen
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Mononuclear Manganese–Peroxo and Bis ACHTUNGTRENNUNG(m-oxo)dimanganese Complexes Bearing a Common N-Methylated Macrocyclic Ligand
Metal–oxygen adducts (Mx Ox, x=1 or 2), such as metal– superoxo, –peroxo, and –oxo species, are key intermediates often detected in the catalytic cycles of dioxygen activation by metalloenzymes. In biomimetic and synthetic chemistry, numerous Mx Ox complexes have been prepared and characterized with various physicochemical methods as structural and functional models of enzymes. Among the Mx O2 ...
متن کاملSynthesis, Characterization, and Reactivity of Cobalt ACHTUNGTRENNUNG(III)–Oxygen Complexes Bearing a Macrocyclic N-Tetramethylated Cyclam Ligand
Oxygen-coordinating metal species, such as metal–peroxo, –hydroperoxo, and –oxo complexes (Scheme 1), have been frequently invoked as reactive intermediates in the catalytic cycles of dioxygen activation by metalloenzymes, such as heme and nonheme iron monooxygenases and copper-containing enzymes. In biomimetic studies, synthetic analogues of these active oxygen intermediates have been intensiv...
متن کامل[Kinetics and mechanisms of the reactions of transition metal complexes].
With the objective of elucidating the mechanisms of dioxygen activation by transition metal complexes, we have investigated functional models of some metalloenzymes, such as phenoxazinone synthase and catechol oxidase, based on bisdimethylglyoximatocobalt(II) and -iron(II) complexes. Kinetic studies and the identification of intermediates permitted to establish a free radical mechanism. The cat...
متن کاملMononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand.
Mononuclear metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are generated as key intermediates in the catalytic cycles of dioxygen activation by heme and non-heme metalloenzymes. We have shown recently that the geometric and electronic structure of the Ni-O2 core in [Ni(n-TMC)(O2)]+ (n = 12 and 14) varies depending on the ring size of the supporting TMC ligand. In this study...
متن کاملPreface to Volume 15 Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases
In this volume of the Metal Ions in Life Sciences series the mastering of dioxygen (O2), methane (CH4), and ammonia (NH3) by mainly manganese-, ironand copper-dependent metalloenzymes and their biomimetic complexes is discussed. It is closely related to Volume 14, The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment, which deals with the biogeochemistry of gases including di...
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تاریخ انتشار 2009