Inorganic Syntheses, Volume 32 by Marcetta York Darensbourg

By Marcetta York Darensbourg

The Inorganic Synthesis sequence offers all clients of inorganic components with designated and foolproof strategies for the coaching of vital and well timed compounds. This new quantity contains details on water-solubilizing ligands for organometallics, labile ligand complexes, and the syntheses of cluster compounds and hydrides.

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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).

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