Abstract

Ab initio calculations at MP2/cc-pVTZ level show that the trifluoromethyl group has a strong destabilizing effect on the nonclassical, σ-bridged cyclobutylmethyl cations. The GIAO-MP2 derived 13C NMR chemical shifts indicate substantial charge delocalization from the neighboring cyclobutyl ring for carbocations with an α-fluorolkyl group as compared to the 1-cyclobutylethyl cation, and this enhanced charge delocalization in case of the α-(trifluoromethyl)cyclobutylmethyl cation would lead to the ring-opening rearrangement to form the relatively more stable nonclassical primary cyclobutylmethyl cation, in which the carbocation center is farthest from the strongly electron-withdrawing trifluoromethyl group.

Department(s)

Chemistry

Keywords and Phrases

Ab initio; Carbocations; Cyclobutylmethyl cation; Fluoroalkyl; GIAO-MP2; Trifluoromethyl

International Standard Serial Number (ISSN)

1551-7012; 1551-7004

Document Type

Article - Journal

Document Version

Final Version

File Type

text

Language(s)

English

Rights

© 2017 Arkat, All rights reserved.

Creative Commons Licensing

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.

Included in

Chemistry Commons

Share

 
COinS