Angular-group-induced bond alternation. I. Origin of the effect from Ab Initio calculations

It is shown that an angular group -XY attached to the benzene ring causes bond length alternation within the ring. This angular-group-induced bond alternation (AGIBA) effect is studied in several mono-substituted benzene derivatives by means of the ab initio calculations. Different alternation patte...

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Bibliographic Details
Published in:Tetrahedron 1997-09, Vol.53 (38), p.13027-13036
Main Authors: Krygowski, Tadeusz M., Wisiorowski, Marcin, Howard, Sean T., Stolarczyk, Leszek Z.
Format: Article
Language:English
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Summary:It is shown that an angular group -XY attached to the benzene ring causes bond length alternation within the ring. This angular-group-induced bond alternation (AGIBA) effect is studied in several mono-substituted benzene derivatives by means of the ab initio calculations. Different alternation patterns are found for angular groups of the -X-Y and -X=Y types. The origin of the AGIBA effect is traced to a competing influence of through-space-π-electron interactions and a rehybridization effect at the substituted carbon atom. The AGIBA effect is shown to be strongly conformation dependent.
ISSN:0040-4020
1464-5416
DOI:10.1016/S0040-4020(97)00826-0