Naslov
Semiempirical AM 1 study of the structural properties in some large fused molecular systems

Autori
Kovaček, Damir ; Margetić, Davor ; Maksić, Zvonimir, B.

Izvornik
Journal of molecular structure. Theochem (0166-1280) 285 (1993), 2; 195-210

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
semiempirical calculations ; Mills-Nixon effect ; AM1

Sažetak
A number of fused molecules exhibiting the Mills-Nixon (MN) effect are examined by the semiempirical AM1 method. The studied compounds include systems involving a naphthalene "aromatic" moiety fused to four- and five-membered rings, annelated biphenylene fragments consisting of alternating aromatic and anti-aromatic rings, and an eight-membered central ring (cyclooctatetraene or cyclooctatetradiyne) flanked by benzene or by benzo-cyclobutane and biphenylene fragments. The structural parameters are in good qualitative agreement with available experimental data. Most of the considered systems exhibit MN distortions which are discussed in terms of -rehybridization and -bond orders. The importance of rehybridization is illustrated by the difference in C-C bond distances within the central ring in all-cis-tris(benzocyclobuta)cyclohexane (7)- a molecule with flat cyclohexane where -electrons are absent in the central six-membered fragment. A difference in stability in angular and linear [3]phenylene is interpreted by synergistic and counteractive interaction of - and -electrons, respectively. The concept of concertedness of - and -electrons resolves the paradox that bent [3]phenylene has a lower total energy in spite of the fact that it is a more localized system than the linear isomer. The primitive graph-theoretical approach based on the "conjugate circuits" model fails completely in this respect.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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