Manganese model oxidation

Kolbel et al. (K16) examined the conversion of carbon monoxide and hydrogen to methane catalyzed by a nickel-magnesium oxide catalyst suspended in a paraffinic hydrocarbon, as well as the oxidation of carbon monoxide catalyzed by a manganese-cupric oxide catalyst suspended in a silicone oil. The results are interpreted in terms of the theoretical model referred to in Section IV,B, in which gas-liquid mass transfer and chemical reaction are assumed to be rate-determining process steps. Conversion data for technical and pilot-scale reactors are also presented. 

The photo-oxidation of n-butane has been modelled by ab initio and DFT computational methods, in which the key role of 1- and 2-butoxyl radicals was confirmed.52 These radicals, formed from the reaction of the corresponding butyl radicals with molecular oxygen, account for the formation of the major oxidation products including hydrocarbons, peroxides, aldehydes, and peroxyaldehydes. The differing behaviour of n-pentane and cyclopentane towards autoignition at 873 K has been found to depend on the relative concentrations of resonance-stabilized radicals in the reaction medium.53 The manganese-mediated oxidation of dihydroanthracene to anthracene has been reported via hydrogen atom abstraction.54 The oxidation reactions of hydrocarbon radicals and their OH adducts are reported.55... 

Mullins CS, Pecoraro V. Reflections on small molecule manganese models that seek to mimic photosynthetic water oxidation chemistry. Coord Chem Rev 2008 252 416-43. 

Active Sites Iron Proteins with Dinuclear Active Sites Manganese The Oxygen-evolving Complex Models Oxidation Catalysis by Transition Metal Complexes Oxygen Inorganic Chentistry. 

The AA(S2-Si) initially obtained by Dekker et af is shown by the curve plotted with solid dots in Fig. 1 (A). This figure also includes the known, in vitro absorbance difference spectra for the gluconates of Mn(IV) and Mn(III) [dashed line] and of Mn(III) and Mn(II) [dotted line], taken from the literature. On the basis of a comparison between AA(S2-Si) and the difference spectra of these manganese model compounds, Dekker etal attributed the absorbance change associated with the S]->S2 transition to the oxidation of Mn(III) to Mn(IV). Note that this interpretation is consistent with that arrived at from X-ray absorption spectroscopy and EPR spectroscopy discussed in the Chapter 19. 

A number of studies have been reported in which a metal atom catalyzes the oxidation of alkenes by PhIO or its derivatives. Three studies have employed iron or manganese model systems for cytochrome P-450 in the oxidation of alkenes. " " [Ru(III) (salen)(X)(Y)] catalyze the oxidation of alkenes by PhIO at room temperature.Similarly, ruthenium(II) complexes of bidentate phosphines may be utilized to promote the epoxidation of alkenes in the presence of iodosylbenzene and in low coordinating media. [Ni(cyclam)] promotes the oxidation of... 

De Wolff model, manganese oxides 89 dead lithium 344 ff Debye length... 

---