By Rudi van Eldik
Advances in Inorganic Chemistry provides well timed and informative summaries of the present development in quite a few topic parts inside inorganic chemistry starting from bio-inorganic to reliable country stories. Thisacclaimed serial positive aspects experiences written by way of specialists within the sector and is an necessary connection with complicated researchers. each one quantity of Advances in Inorganic Chemistry comprises an index, and every bankruptcy is totally referenced. . finished reports written via prime specialists within the box . An crucial connection with complicated researchers . comprises 7 contributions overlaying very important advances in inorganic chemistry
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19)^(20). The measured rate constant in the presence of (NH3)5CoBr2 þ then becomes k19. The dramatic e¡ect of (NH3)5CoBr2 þ in Fig. 10 suggests that both Cr2þ aq and CMe3CO may be responsible for the complex behavior under air-free conditions. In O2 -saturated solutions, a major portion of acyl radicals (60^80%) react with O2 as in Eq. (22), the rest undergoing decarbonylation and ¢nally formation of tert-butylperoxyl radicals, Eqs. (20) and (23). The source of CraqO2 þ , which is clearly an intermediate on the basis of the e¡ects of methanol and Mn2þ aq , is reaction 24.
Biol. 2002, 6, 556^567. 9. McLain, J. ; Groves, J. T. Biomimetic oxygenations related to cytochrome P450: metal-oxo and metal-peroxo intermediates, ‘‘Biomimetic Oxidations Catalyzed by Transition Metal Complexes’’; Ed. ; Imperial College Press: London, 2000, pp. 91^169. 10. Groves, J. ; Lee, J. Oxometalloporphyrins in oxidative catalysis, ‘‘The Porphyrin Handbook. Volume 4. Biochemistry and Binding: Activation of Small Molecules’’; Eds. Kadish, K. ; Smith, K. ; Academic Press: San Diego, 2000, pp.
Copyright 2000 American Chemical Society. ATOM TRANSFER AND FREE RADICAL CHEMISTRY 23 The overall kinetic behavior, and the e¡ects of methanol, Mn2þ aq , and (NH3)5CoBr2 þ suggest a mechanism consisting of an initial bimolecular reaction, most likely abstraction of the aldehydic hydrogen by CraqOO2 þ , to generate acyl radicals and CraqOOH2 þ . Subsequent steps generate additional intermediates (CraqO2 þ , Cr2þ aq , acylperoxyl and alkylperoxyl radicals) which can be either removed or prevented from forming by use of various scavengers.
Advances in Inorganic Chemistry, Vol. 55 by Rudi van Eldik