Reactivity of aqueous Fe(IV) in hydride and hydrogen atom transfer reactions

被引：262
作者：
Pestovsky, O [1 ]
Bakac, A [1 ]
机构：
[1] Iowa State Univ Sci & Technol, Ames Lab, Ames, IA 50011 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 42期
关键词：
D O I：
10.1021/ja0457112
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Oxidation of cyclobutanol by aqueous Fe(IV) generates cyclobutanone in similar to70% yield. In addition to this two-electron process, a smaller fraction of the reaction takes place by a one-electron process, believed to yield ring-opened products. A series of aliphatic alcohols, aldehydes, and ethers also react in parallel hydrogen atom and hydride transfer reactions, but acetone and acetonitrile react by hydrogen atom transfer only. Precise rate constants for each pathway for a number of substrates were obtained from a combination of detailed kinetics and product studies and kinetic simulations. Solvent kinetic isotope effect for the self-decay of Fe(IV), k(H2O)/k(D2O) = 2.8, is consistent with hydrogen atom abstraction from water.
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页码：13757 / 13764
页数：8
相关论文
共 53 条
[1]  
[Anonymous], UNPUB
[2]   MECHANISTIC AND KINETIC ASPECTS OF TRANSITION-METAL OXYGEN CHEMISTRY [J].
BAKAC, A .
PROGRESS IN INORGANIC CHEMISTRY, VOL 43, 1995, 43 :267-351
[3]  
BOTHE E, 1983, Z NATURFORSCH B, V38, P212
[4]  
BOTHE E, 1980, Z NATURFORSCH B, V35, P1035
[5]   MECHANISM OF 1ST ORDER DECAY OF 2-HYDROXY-PROPYL-2-PEROXYL RADICALS AND OF O2- FORMATION IN AQUEOUS-SOLUTION [J].
BOTHE, E ;
BEHRENS, G ;
SCHULTEFROHLINDE, D .
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1977, 32 (08) :886-889
[6]   CRITICAL-REVIEW OF RATE CONSTANTS FOR REACTIONS OF HYDRATED ELECTRONS, HYDROGEN-ATOMS AND HYDROXYL RADICALS (.OH/.O-) IN AQUEOUS-SOLUTION [J].
BUXTON, GV ;
GREENSTOCK, CL ;
HELMAN, WP ;
ROSS, AB .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1988, 17 (02) :513-886
[7]   Dioxygen activation at mononuclear nonheme iron active sites: Enzymes, models, and intermediates [J].
Costas, M ;
Mehn, MP ;
Jensen, MP ;
Que, L .
CHEMICAL REVIEWS, 2004, 104 (02) :939-986
[8]   Oxidizing species in the mechanism of cytochrome P450 [J].
de Montellano, PRO ;
De Voss, JJ .
NATURAL PRODUCT REPORTS, 2002, 19 (04) :477-493
[9]   Reaction of ozone with ethene and its methyl- and chlorine-substituted derivatives in aqueous solution [J].
Dowideit, P ;
von Sonntag, C .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1998, 32 (08) :1112-1119
[10]   Mononuclear (nitrido)iron(V) and (oxo)iron(IV) complexes via photolysis of [(cyclam-acetato)FeIII(N3)]+ and ozonolysis of [(cyclam-acetato)FeIII(O3SCF3)]+ in water/acetone mixtures [J].
Grapperhaus, CA ;
Mienert, B ;
Bill, E ;
Weyhermüller, T ;
Wieghardt, K .
INORGANIC CHEMISTRY, 2000, 39 (23) :5306-5317
123456