Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism
文献类型：期刊论文
| 作者 | Qu, ZW; Zhu, H; Zhang, XK; Zhang, QY |
| 刊名 | JOURNAL OF COMPUTATIONAL CHEMISTRY
 |
| 出版日期 | 2003-02-01 |
| 卷号 | 24期号:3页码:340-344 |
| 关键词 | Density Functional Calculations Reaction Mechanism Cyclobutane Radical Anion Cycloreversion |
| ISSN号 | 0192-8651 |
| DOI | 10.1002/jcc.10177 |
| 英文摘要 | The 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. |
| 语种 | 英语 |
| WOS记录号 | WOS:000180788200008 |
| 出版者 | JOHN WILEY & SONS INC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/80631]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Qu, ZW |
| 作者单位 | 1.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 |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：化学研究所
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