A non-least motion pathway for 1,2-shift in cyclic vinyl cations

Jemmis, E. D. ; Sarma, K. S. ; Pavankumar, P. N. V. (1985) A non-least motion pathway for 1,2-shift in cyclic vinyl cations Journal of Molecular Structure: Theochem, 121 . pp. 305-311. ISSN 0166-1280

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/016612...

Related URL: http://dx.doi.org/10.1016/0166-1280(85)80070-1


Qualitative molecular orbital arguments are presented to support a novel non-least motion pathway for 1,2-migrations in cyclic vinyl cations. Ab initio calculations using a split valence 3-21G basis set on the bridged vinyl cation with varying HCC angle θ (5) show that the bridging hydrogen moves out of the C2H2 plane at θ less than 170°. This is due to the decreased interaction of the bridging group or atom with the distorted π bond. Semi-empirical calculations using the MINDO/3 method were carried out on the classical and two types of bridged structures for the cyclopentenyl cation. The transition state corresponding to the non-least motion pathway is found to be of lower energy than that for the least motion pathway.

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