Dioxygen, activation metalled

Dioxygen activation in transition metal complexes in the light of molecular orbital calculations. R. Boca, Coord. Chem. Rev., 1983, 50,1-72 (245). 

Simandi LI (2003) Advances in catalytic activation of dioxygen by metal complexes. Kluwer, Dordrecht... 

Dioxygenases often have broad substrate specificity and require only a minimal characteristic structure for substrate recognition [310], Transition metal or an organic cofactor mediates dioxygen activation needed by the oxygenases action. Iron and copper, in their lower oxidation states are the metals most commonly used, but also organic co-factors like dihydroflavin and tetrahydropterin are able to activate the oxygen molecule. 

L.I. Simandi (ed.) Catalytic Activation of Dioxygen by Metal Complexes. 1992... 

Dioxygen Activation by Transition Metal Complexes. Atom Transfer and Free Radical Chemistry in Aqueous Media... 

The original method of polymers stabilization was invented by Gladyshev and coworkers [14-18]. They proposed to introduce in polymer a metal compound inert toward dioxygen. This compound is decomposed at elevated temperatures with production of a thin metal powder. Formates, oxalates, and carbonyls of metals were suggested as predecessors of an active metal powder. For example, ferrous oxalate decomposes at 600-630 K with the formation of pyrofore iron and ferrous oxide... 

The irreversible coordination of dioxygen to metal complexes is of remarkable importance in order to explain the activity of enzymes such monooxygenases, dioxygenases and cytochrome c oxidase. 

Ezhova, M. B. James, B. R. in Advances in Catalytic Activation of Dioxygen by Metal Complexes , Ed. Simandi, L. S. Volume 26, Catalysis by Metal Complexes, Kluwer Academic Publishers, Dordrecht, 2003. 

Theopold KH (2007) Dioxygen Activation by Organometallics of Early Transition Metals. 22 17-37... 

The enzymes of this type that have been characterized contain some type of redox-active cofactor, such as a flavin (3), or a metal ion (heme iron, non-heme iron, or copper), or both (4-6). Our understanding of the mechanism of these enzymes is most advanced in the case of the heme-containing enzyme cytochrome P450. But in spite of the availability of a crystal structure of an enzyme-substrate complex (7) and extensive information about related reactions of low molecular weight synthetic analogues of cytochrome P450 (8), a detailed picture of the molecular events that are referred to as "dioxygen activation" continues to elude us. 

Ezhova MB, James BR (2003) In Simandi LI (ed) Adavnces in catalytic activation of dioxygen by metal complexes. Kluwer, Netherlands, pp 1-77 Meyer TJ, Huynh MHV (2003) Inorg Chem 42 8140-8160 Simmoneaux G, Le Maux P (2002) Coordin Chem Rev 228 43-60 Watanabe Y, Fuji H (2000) Struct Bonding 97 61-89... 

Dioxygen Activation by Organometallics of Early Transition Metals... 

Once the oxidative-addition reaction of dioxygen to metal d -ions has occurred, the essentially electrophihc dioxygen becomes a nucleophilic peroxide ligand. Since the oxidation of substrates is associated with electron transfer from the substrate to the oxidant, i.e. in this case the dioxygen adduct, effective oxygenations require a further activation to transform the nucleophihc peroxide into an electrophihc species prior to the oxygen transfer. 

Tejel C, Ciriano MA (2007) Catalysis and Organometallic Chemistry of Rhodium and Iridium in the Oxidation of Organic Substrates. 22 97-124 Tekavec TN, Louie J (2006) Transition Metal-Catalyzed Reactions Using N-Heterocyclic Carbene Ligands (Besides Pd- and Ru-Catalyzed Reactions). 21 159-192 Theopold KH (2007) Dioxygen Activation by Organometallics of Early Transition Metals. 22 17-37... 

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