Abstract
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.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.