An analysis of the σ-, π- and total current density maps, calculated using a distributed-origin coupled Hartree-Fock method, of the non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAH) acenaphthylene (1), pyracylene (2), fluoranthene (3) and cyclopenta[cd]fluoranthene (4) shows that, whereas the presence of a single pentagon in 1 and 3 has only minor effects on the core naphthalene unit, the strong cooperative effect of the two pentagons connected by a formal double bond in 2 and 4 results in intense paratropic currents in the pentagons, and markedly reduced aromaticity according to conventional criteria. The accuracy of the all-electron maps is supported by calculation of 1H and 13C NMR chemical shifts in agreement with experiment and their interpretation is consistent with nucleus-independent chemical shifts (NICS values). It is shown that the pattern of paratropic contributions can be explained qualitatively within Hückel-London π-electron theory.
Mapping the modification of ring currents induced by cyclopentafusion on a naphthalene core / Fowler P.W.; Steiner E.; Acocella A.; Jenneskens L.W.; Havenith R.W.A.. - In: JOURNAL OF THE CHEMICAL SOCIETY. PERKIN TRANSACTIONS 2. - ISSN 1472-779X. - ELETTRONICO. - 7:(2001), pp. 1058-1065. [10.1039/b102413m]
Mapping the modification of ring currents induced by cyclopentafusion on a naphthalene core
Acocella A.;
2001
Abstract
An analysis of the σ-, π- and total current density maps, calculated using a distributed-origin coupled Hartree-Fock method, of the non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAH) acenaphthylene (1), pyracylene (2), fluoranthene (3) and cyclopenta[cd]fluoranthene (4) shows that, whereas the presence of a single pentagon in 1 and 3 has only minor effects on the core naphthalene unit, the strong cooperative effect of the two pentagons connected by a formal double bond in 2 and 4 results in intense paratropic currents in the pentagons, and markedly reduced aromaticity according to conventional criteria. The accuracy of the all-electron maps is supported by calculation of 1H and 13C NMR chemical shifts in agreement with experiment and their interpretation is consistent with nucleus-independent chemical shifts (NICS values). It is shown that the pattern of paratropic contributions can be explained qualitatively within Hückel-London π-electron theory.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
