ICCAS OpenIR
Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism
Qu, ZW; Zhu, H; Zhang, XK; Zhang, QY
2003-02-01
Source PublicationJOURNAL OF COMPUTATIONAL CHEMISTRY
ISSN0192-8651
Volume24Issue:3Pages:340-344
AbstractThe mechanism of cycloreversion of cyclobutane radical anion (c-C4H8-) has been investigated at the UB3LYP/6-31++G(d,p) level, and compared with those of neutral c-C4H8 and c-C4H8+ radical cation. Although both c-C4H8- and C2H4 are shown to be Rydberg states unstable with respect to electron ejection, the activation barrier for the "rotating" cycloreversion of c-C4H8- (37.3 kcal/mol) is lower by about 25.2 kcal/mol than that of c-C4H8, and even the, intervention of tetramethylene radical anion intermediate may reduce the activation barrier for the cycloreversion of c-C4H8 by about 8.4 kcal/mol, mainly due to stronger electron-deficiency of intermediate biradical species than close-shell cyclobutanes. For the cycloreversion for c-C4H8-, side isomerization reaction may be efficiently prevented by the low kinetic stability of tetramethylene radical anion intermediate towards dissociation, just different from the radical cation case. Our theoretical results have suggested the possibility of electron-attachment catalysis of the cycloreversion of some electron-deficient substituted cyclobutanes. (C) 2003 Wiley Periodicals, Inc.
KeywordDensity Functional Calculations Reaction Mechanism Cyclobutane Radical Anion Cycloreversion
DOI10.1002/jcc.10177
Indexed BySCI
Language英语
WOS IDWOS:000180788200008
PublisherJOHN WILEY & SONS INC
Citation statistics
Cited Times:2[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/80632
Collection中国科学院化学研究所
Corresponding AuthorQu, ZW
Affiliation1.Chinese Acad Sci, Inst Chem, Ctr Mol Sci, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China
2.Jilin Univ, Inst Theoret Chem, Changchun 130023, Peoples R China
Recommended Citation
GB/T 7714
Qu, ZW,Zhu, H,Zhang, XK,et al. Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2003,24(3):340-344.
APA Qu, ZW,Zhu, H,Zhang, XK,&Zhang, QY.(2003).Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism.JOURNAL OF COMPUTATIONAL CHEMISTRY,24(3),340-344.
MLA Qu, ZW,et al."Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism".JOURNAL OF COMPUTATIONAL CHEMISTRY 24.3(2003):340-344.
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