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Synlett 2003(7): 0922-0936
DOI: 10.1055/s-2003-39284
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© Georg Thieme Verlag Stuttgart ˙ New York

Angular Group Induced Bond Alternation (AGIBA). A New Face of Substituent Effect Detected in Molecular Geometry

Tadeusz Marek Krygowski*, Micha Ksawery Cyrański
Department of Chemistry, University of Warsaw, L. Pasteura 1, 02-093 Warsaw, Poland
Fax: +48(22)8222892; e-Mail: tmkryg@chem.uw.edu.pl;
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Publication History

Received 7 March 2002
Publication Date:
20 May 2003 (online)

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Abstract

Angular Group Induced Bond Alternation is a new face of a substituent effect well documented by careful analysis of molecular geometry. The angular groups attached to monocyclic 6-π-electron systems cause substantial changes to π-electron distribution in the ring. Different patterns are found for X-Y and X=Y types of groups. The overall effect is due to the rehybridization effect, the through space π-electron interactions between a group and the ring, possibly also by other subtle effects, eg. the negative hyperconjugation. The effect is strongly conformational dependent. While the AGIBA is energetically weak, it is structurally strong enough that other interactions in monocyclic systems, eg. through - resonance type interactions do not reduce it. In polycyclic benzenoid hydrocarbons AGIBA works only locally while in non-cyclic π-electron systems the effect does not work at all.

Key words

AGIBA - substituent effects - benzene derivatives - π-electron systems

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