Read e-book online Advances in Inorganic Chemistry, Vol. 55 PDF

By Rudi van Eldik

ISBN-10: 0120236559

ISBN-13: 9780120236558

Advances in Inorganic Chemistry offers well timed and informative summaries of the present growth in a number of topic parts inside inorganic chemistry starting from bio-inorganic to strong country experiences. Thisacclaimed serial positive factors studies written through specialists within the zone and is an crucial connection with complicated researchers. each one quantity of Advances in Inorganic Chemistry includes an index, and every bankruptcy is absolutely referenced. . entire experiences written via top specialists within the box . An fundamental connection with complex researchers . contains 7 contributions protecting vital advances in inorganic chemistry

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The recently estimated rate constants (116,161) for the identity reactions kt-BuO/t-BuOH (3 Â 104 MÀ1 sÀ1) and kt-BuOO/t-BuOOH (5 Â 102 MÀ1 sÀ1) in non-aqueous solvents di¡er by a factor of $ 60, which will cause only a modest, 8 -fold increase in the estimated kt-BuO/kt-BuOO. 5 $ 1 is probably also correct to within an order of magnitude. The ¢ndings in this work are very much in line with several related studies on hydrogen atom abstraction by non-radical metal-oxo species (113,117,162) in addition to oxygen-centered radicals.

The reason probably lies in the short lifetime of NO2, which rapidly disproportionates to nitrite and nitrate, see Scheme 12, Eqs. 5 Â 107 MÀ1 sÀ1, Eq. (57). Direct kinetic studies are thus limited to rapid reactions and require the use of absorbing reactants or kinetic probes. NOÀ 3 þ HNO2 þ H ð57Þ One of the advantages of chromium complexes over those of, say, cobalt or rhodium in mechanistic studies is the much greater photoinertness of the chromium family. The superoxochromium CraqOO2 þ , for example, is almost una¡ected by the >320 nm light, but the superoxides of cobalt and rhodium photohomolyze readily even when exposed to visible light, <500 nm.

1999, pp. 303^321. 14. ; Mizoguchi, T. ; Lippard, S. J. Coord. Chem. Rev. 2000, 200^202, 443^485. 15. ; Gherman, B. ; Lippard, S. ; Friesner, R. A. Curr. Op. Chem. Biol. 2002, 6, 236^242. 16. Kopp, D. ; Lippard, S. J. Curr. Op. Chem. Biol. 2002, 6, 568^576. 17. Lipscomb, J. ; Que, L. Jr. J. Biol. Inorg. Chem. 1998, 3, 331^336. 18. Shteinman, A. A. J. Biol. Inorg. Chem. 1998, 3, 325^330. 19. Que, L. ; Tolman, W. B. Angew. Chem. Int. Ed. 2002, 41, 1114^1137. 20. Blackman, A. ; Tolman, W. B. Struct.

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Advances in Inorganic Chemistry, Vol. 55 by Rudi van Eldik

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