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Thermodynamic stabilities of carbon-and nitrogen-centered radicals 被引量:1

Thermodynamic stabilities of carbon-and nitrogen-centered radicals
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摘要 The gas-phase homolytic C-H and N-H bond dissociation energies(BDE)of the substi-tuted phenoacetonitrile families,aromatic amines,and semicarbazone derivatives were systematically investigatedor reinvestigated based on a cycle utilizing the thermodynamic quantities determined in DMSO solution.Theexperimental evidence collected in.this work dearly indicates that the radicals derived from the above familiesare of the‘Class O’type,i.e.to be stabilized by a remote electron-donating substituent but destabilized by anelectron-withdrawing substituent. <正> The gas-phase homolytic C-H and N-H bond dissociation energies(BDE)of the substi-tuted phenoacetonitrile families,aromatic amines,and semicarbazone derivatives were systematically investigatedor reinvestigated based on a cycle utilizing the thermodynamic quantities determined in DMSO solution.Theexperimental evidence collected in.this work dearly indicates that the radicals derived from the above familiesare of the‘Class O’type,i.e.to be stabilized by a remote electron-donating substituent but destabilized by anelectron-withdrawing substituent.
出处 《Science China Chemistry》 SCIE EI CAS 1995年第12期1417-1424,共8页 中国科学(化学英文版)
关键词 homolytic bond DISSOCIATION energy RADICAL stability SUBSTITUENT effect. homolytic bond dissociation energy radical stability substituent effect.
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  • 1赵永昱,还振威,程津培.苯乙酮缩氨脲类化合物及其正负离子基的氮氢键的断裂能[J].化学学报,1994,52(10):980-984. 被引量:2
  • 2BORDWELL F G,ZHANG Xianman,CHENG Jinpei.Bond dissociation energies of the nitrogen-hydrogen bondsin anilines and in the corresponding radical anions:equi-librium acidities of aniline radical cations. Journal of Organic Chemistry . 1993
  • 3Cheng JP and Zhao Y.Homolytic bond cleavage energies of the acidic N H bonds in dimethyl sulfoxide solution andpropertiesofthe corresponding radicalsand radicalcations. Tetrahedron . 1993
  • 4Parker,V. D.Homolytic bond (H-A) dissociation free energies in solntion--Application of the standard potenlial of the (H~+/H) couple, J. Journal of the American Chemical Society . 1992
  • 5Bamberger,E.Under die Reduction der Nitroverbindungen, Ber. 1894, 27: 1347; Under das-Phenylhydroxylamin, Ber .
  • 6Walter,R,I.Substituent effects on the properties of stable aromatic free radicals, J. Journal of the American Chemical Society . 1966
  • 7Bamberger, E,Baudisch, O.Einwirkung von Hydroperoxyd auf Nitroso-Acetanilid und notizüber Selbstzersetzung des Letzteren. Ber . 1909
  • 8Bordwell, F. G,Zhang, X.-M.From equilibrium acidities to radical stabilization energies. Accounts of Chemical Research . 1993
  • 9McMiller, D. E,Golden, D. M.Hydrocarbon bond dissociation energies. Annual Review of Physical Chemistry . 1982
  • 10Bordwell, F. G,Cheng, J.-P.Substituent effects on the stabilities of phenoxyl radicals. Journal of the American Chemical Society . 1991

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