Density functional investigation on electron-transfer catalysis of cycloreversion of cyclobutane: Radical anion mechanism

• Published in: Journal of computational chemistry 2003-02, Vol.24 (3), p.340-344
• Main Authors: Qu, Zheng-Wang, Zhu, Hui, Zhang, Xing-Kang, Zhang, Qi-Yuan
• Format: Article
• Language: English
• Subjects: cyclobutane; cycloreversion; density functional calculations; radical anion; reaction mechanism
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.10177

The mechanism of cycloreversion of cyclobutane radical anion (c‐C4H 8−) has been investigated at the UB3LYP/6‐31++G(d,p) level, and compared with those of neutral c‐C4H8 and c‐C4H 8+ radical cation. Although both c‐C4H 8− and C2H4 are shown to be Rydberg states unstable with respect to electron ejection, the activation barrier for the “rotating” cycloreversion of c‐C4H 8− (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‐C4H 8−, 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. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 340–344, 2003