Molybdenum oxide, isotopic oxygen

As for the reactions catalyzed by members of this third family of molybdenum enzymes, there are several variations from the principal theme of oxygen atom transfer. Formate dehydrogenase from E. coli catalyzes the oxidation of formate to CO2, a reaction that isotope studies have shown does not pass through a bicarbonate intermediate (Khangulov et al., 1998). Instead, it appears likely that C02is formed by direct hydride transfer from substrate to the molybdenum center. Polysulfide reductase is another molybdenum enzyme that catalyzes a non-canonical reaction the... 

Duan, Y., Anbar, A.D., Arnold, G.L., Lyons, T.W., Gordon, G.W., and Kendall, B. (2010) Molybdenum isotope evidence for mild environmental oxygenation before the Great Oxidation Event. Geochim. Cosmochim. Acta, 74 (23), 6655-6668. 

Oxo-transfer reactions involving molybdenum have been reviewed. The structure of trans-[Ru(0)2(py)2(0Ac)2] shows a relatively long Ru=0 bond which may be important in the role of the complex as an oxo-transfer reagent. Kinetics and mechanisms for epoxidations by [Ru(terpy)(tmen) (H20)] have been reported. Molecular orbital calculations on the formation of epoxides from Ru(IV)=0 and ethene suggest that the preferred pathway involves a nucleophilic attack on the oxo oxygen. Similar studies have been carried out on the oxidation of alcohols. The mechanism of oxidation of alcohols by [Ru OL] " where HL=[2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine has been investigated. The reactions are first-order in both reagents, and kinetic isotope effects on the... 

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