ICCAS OpenIR
Cycloreversion of formylcyclobutane radical anion: Two-step rotating mechanism
Qu, ZW; Zhu, H; Zhang, RB; Zhang, XD; Ai, XC; Zhang, XK; Zhang, QY
2004-06-17
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume108Issue:24Pages:5253-5257
AbstractThe [2+2] cycloreversion reaction of formylcyclobutane radical anion (c-C4H7-CHO.-) has been investigated at the UB3LYP level with the augmented Dunning's correlation-consistent polarized valence double-zeta basis set supplied with four even-tempered sp shells. Very diffuse p-pi*-like singly occupied orbitals (SOMO) are found for the c-C4H7-CHO.- and product CH2CHCHO.- radical anions, necessitating the use of a rather diffuse basis set for mechanistic study. The respective electron affinities of c-C4H7-CHO and CH2CHCHO are calculated to be 5.4 and 16.1 kcal/mol, showing the ability to bind an extra electron. The intermediate structure (.)(CH2)(3)CHCHO- is found to be a valence-bound distonic anion apt to the elimination of C2H4. The present two-step "rotating" cycloreversion mechanism for c-C4H7-CHO.- is formally similar to the biradical one for neutral cyclobutane structures, but with evidently lower potential barrier. For efficient electron-attachment catalysis, the extra electron should be trapped by suitable functional groups in some orbitals with substantial overlap with the sigma*-orbitals of the cyclobutane structure.
DOI10.1021/jp031307y
Indexed BySCI
Language英语
WOS IDWOS:000221965300018
PublisherAMER CHEMICAL SOC
Citation statistics
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/82272
Collection中国科学院化学研究所
Corresponding AuthorQu, ZW
Affiliation1.Chinese Acad Sci, State Key Lab Struct Chem Unstable & Stable Speci, Ctr Mol Sci, Inst Chem, Beijing 100080, Peoples R China
2.Max Planck Inst Stromungsforsch, D-37073 Gottingen, Germany
Recommended Citation
GB/T 7714
Qu, ZW,Zhu, H,Zhang, RB,et al. Cycloreversion of formylcyclobutane radical anion: Two-step rotating mechanism[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2004,108(24):5253-5257.
APA Qu, ZW.,Zhu, H.,Zhang, RB.,Zhang, XD.,Ai, XC.,...&Zhang, QY.(2004).Cycloreversion of formylcyclobutane radical anion: Two-step rotating mechanism.JOURNAL OF PHYSICAL CHEMISTRY A,108(24),5253-5257.
MLA Qu, ZW,et al."Cycloreversion of formylcyclobutane radical anion: Two-step rotating mechanism".JOURNAL OF PHYSICAL CHEMISTRY A 108.24(2004):5253-5257.
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