Metal-catalyzed water oxidation iron catalysts

The [TPPFeCl] -NaBITi system in diglyme has been shown to perform remarkably efficiently as a catalyst for the reduction of nitrobenzenes to anilines. Although both TPPCo and TPPMnCl also catalyze the reduction of p-chloronitrobenzene to jo-chloroaniline, their catalytic activities are much lower thanthatofTPPFeCl. Anothertype of reduction catalyst, in this case of dioxygen to water, begins with carbon-supported chloroiron(ni) tetramethoxyphenylporphyrin, which is then heat-treated at 900 °C for one h." This causes decomposition of the porphyrin to produce metallic, carbidic and oxidic iron, as detected by Mossbauer spectroscopy. The active... 

A mild aerobic palladium-catalyzed 1,4-diacetoxylation of conjugated dienes has been developed and is based on a multistep electron transfer46. The hydroquinone produced in each cycle of the palladium-catalyzed oxidation is reoxidized by air or molecular oxygen. The latter reoxidation requires a metal macrocycle as catalyst. In the aerobic process there are no side products formed except water, and the stoichiometry of the reaction is given in equation 19. Thus 1,3-cyclohexadiene is oxidized by molecular oxygen to diacetate 39 with the aid of the triple catalytic system Pd(II)—BQ—MLm where MLm is a metal macrocyclic complex such as cobalt tetraphenylporphyrin (Co(TPP)), cobalt salophen (Co(Salophen) or iron phthalocyanine (Fe(Pc)). The principle of this biomimetic aerobic oxidation is outlined in Scheme 8. 

As a matter of fact, olefin-consuming reactions (by H2) may be a serious problem in some technical reactions. Palladium complexes and Co2(CO)g (commercial products) are typical catalysts. Problems may also arise in the Fischer-Tropsch reaction [19, 20] where iron oxides of a certain basicity (alkaline-metal doping) are being used to catalyze the formation of hydrocarbons according to (the simplified) eq. (15). More details are provided in Section 3.1.8. Since water is inevitably formed, carbon dioxide can also occur. On the other hand, it is doubtful whether the CO/H2O system will be used for directed reductions of organic compounds, since hydrogen is an extremely abundant industrial chemical. The water-gas shift reaction is thus to be avoided in the vast majority of cases. 

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