Including Bioinorganic Studies by van Eldik R. (eds.)

By van Eldik R. (eds.)

Advances in Inorganic Chemistry provides well timed and informative summaries of the present growth in numerous topic components inside inorganic chemistry starting from bio-inorganic to sturdy nation stories. Thisacclaimed serial good points experiences written by means of specialists within the sector and is an necessary connection with complicated researchers. each one quantity of Advances in Inorganic Chemistry includes an index, and every bankruptcy is absolutely referenced. . complete studies written by means of top specialists within the box . An integral connection with complicated researchers . comprises 7 contributions protecting very important advances in inorganic chemistry. learn more... summary: Advances in Inorganic Chemistry offers well timed and informative summaries of the present development in numerous topic parts inside inorganic chemistry starting from bio-inorganic to strong nation reports. Thisacclaimed serial gains experiences written by means of specialists within the sector and is an crucial connection with complex researchers. each one quantity of Advances in Inorganic Chemistry comprises an index, and every bankruptcy is absolutely referenced. . entire reports written by means of top specialists within the box . An vital connection with complex researchers . contains 7 contributions protecting vital advances in inorganic chemistry

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The ¢rst-order ¢t of data in (b) is also shown. Reproduced with permission from J. Am. Chem. Soc. 2000, 122, 1092^1097. 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.

CraqOO2 þ /CMe3C(O)OO cross reaction The chemistry in Eq. (24) is believed to take place by an initial radical coupling between the terminal oxygen of CraqOO2 þ and acylperoxyl radicals. A direct study of the analogous reaction between CraqOO2 þ and acetylperoxyl radicals was carried out recently (149). For the purpose of product analysis, CH3C(O)OO was generated in the reaction between CraqOO2 þ and CH3CHO. The reaction produced large amounts of 2þ HCrOÀ ). The yield decreased only marginally 4 (43% of total CraqOO (to 35%) in the presence of added Mn2þ aq .

J. Angew. Chem. Int. Ed. 2001, 40, 2782^2807. 5. Solomon, E. ; Palmer, A. E. Angew. Chem. Int. Ed. 2001, 40, 4570^4590. 6. Guengerich, F. P. Biolog. Chem. 2002, 383, 1553^1564. 7. -D. Top. Curr. Chem. 1997, 184, 39^96. 8. ; de Visser, S. ; Schroeder, D. Curr. Op. Chem. 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.

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