By Rudi van Eldik, Jan Reedijk
Advances in Inorganic Chemistry quantity 58 specializes in homogeneous biomimetic oxidation catalysis. Contributions by means of major specialists within the box disguise vital advances in inorganic and bioinorganic chemistry. Contributions contain diversity-based techniques to selective biomimetic oxidation catalysis; the selective conversion of hydrocarbons with H2O2 utilizing biomimetic non-heme iron and manganese oxidation catalysis; DNA oxidation through copper and manganese complexes; impacts of the ligand in copper-dioxygen complex-formation and substrate oxidations; biomimetic oxidations by way of dinuclear and trinuclear copper complexes. within the ultimate contribution the authors specialise in eco-friendly oxidation of alcohols utilizing biomimetic copper complexes and enzymes as catalysts. quantity fifty eight offers one other welcomed addition to the generally acclaimed sequence, Advances in Inorganic Chemistry.
* contains new details at the very important advances in inorganic and bioinorganic chemistry
* each one bankruptcy is totally referenced
* includes accomplished stories written by way of top specialists within the box
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Extra resources for Advances in Inorganic Chemistry, Volume 58: Homogeneous Biomimetic Oxidation Catalysis
7. Possible pathways for the decomposition of FeIII^OOH transient intermediates (10). decomposition of H2O2 (Eqs. (4) and (5)), and the other involving a metalbased oxidant formed by decomposition of a FeIII^OOH transient intermediate (Fig. 7) (43^45). In the presence of an organic substrate, the highly reactive hydroxyl radical generated by Eq. (4) and both FeII and FeIII ions (Eqs. (4) and (5)) enters into a series of consecutive reactions that lead to substrate oxidation (46). Usually, the oxidation reactions that are carried out using excess of H2O2 relative to the iron catalyst typically yield large amounts of free radicals due to the rapid reaction of the iron intermediates with H2O2.
Complexes with two cis-open coordination sites (Fig. 15) like [Fe(tpa)(CH3CN)2](ClO4)2, [Fe(tpa)(OTf)2], [Fe(6 -Me3 -tpa) (CH3CN)2](ClO4)2, [Fe(6 -Me3 -tpa)(OTf)2], [Fe(bpmen)(CH3CN)2](ClO4)2, [Fe (6 -Me2 -bpmen)(OTf)2], and [Fe(6 -Me2 -bpmen)(OTf)2], not only catalyze the epoxidation of ole¢ns but also the cis-dihydroxylation reaction (85^88). Employing the complex [Fe(6 -Me3 -tpa)(CH3CN)2](ClO4)2, which contains two cis-coordinated acetonitrile molecules, the cis-diol was observed as the major product in the oxidation of cyclooctene (87).
C KIEd 38/28e Ref. 4 ^ 6 (53) (70) (70) (70) (71,72) (98) (77) (79) (78) (198) (84) (199) (69) (69) (83) a Reactions performed in acetonitrile. A/K ¼ cyclohexanol to cyclohexanone ratio in the oxidation of cyclohexane c E⁄ciency based on H2O2. d Kinetic isotope e¡ect of cyclohexanol formation. e 1-adamantanol/(2 -adamantanol þ 2 -adamantanone) in the oxidation of corrected for the number of C^H bonds in a group. b adamantane dismutation of H2O2 (53). To prevent the formation of inactive iron(II) species during the catalytic cycle, Fontecave and co-workers have isolated a m-oxo diiron(III) complex containing a hindered chiral bipyridine derivative (71).