In this work, we have analyzed the local aromaticity of the six-membered rings (6-MRs) of planar and pyramidalized pyracylene species through the structurally based harmonic oscillator model of aromaticity (HOMA), the electronically based para-delocalization index (PDI), and the magneticbased nucleus independent chemical shift (NICS) measurements, as well as with maps of ring current density. According to ring currents and PDI and HOMA indicators of aromaticity, there is a small reduction of local aromaticity in the 6-MRs of pyracylene with a bending of the molecule. In the case of NICS, the results depend on whether the NICS value is calculated at the center of the ring (NICS(0)) or at 1 Å above (NICS(1)out) or below (NICS(1)in) the ring plane. While NICS- (1)out values also indicate a slight decrease of aromaticity with bending, NICS(0) and NICS(1)in wrongly point out a large increase of aromaticity upon distortion. We have demonstrated that the NICS(0) reduction in the 6-MRs of pyracylene upon bending is due to (a) a strong reduction of the paratropic currents in 5-MRs and (b) the fact that, due to the distortion, the paratropic currents point their effects in other directions.

Local Aromaticity of the Six-Membered Rings in Pyracylene. A Difficult Case for the NICS Indicator of Aromaticity

ZANASI, Riccardo
2004-01-01

Abstract

In this work, we have analyzed the local aromaticity of the six-membered rings (6-MRs) of planar and pyramidalized pyracylene species through the structurally based harmonic oscillator model of aromaticity (HOMA), the electronically based para-delocalization index (PDI), and the magneticbased nucleus independent chemical shift (NICS) measurements, as well as with maps of ring current density. According to ring currents and PDI and HOMA indicators of aromaticity, there is a small reduction of local aromaticity in the 6-MRs of pyracylene with a bending of the molecule. In the case of NICS, the results depend on whether the NICS value is calculated at the center of the ring (NICS(0)) or at 1 Å above (NICS(1)out) or below (NICS(1)in) the ring plane. While NICS- (1)out values also indicate a slight decrease of aromaticity with bending, NICS(0) and NICS(1)in wrongly point out a large increase of aromaticity upon distortion. We have demonstrated that the NICS(0) reduction in the 6-MRs of pyracylene upon bending is due to (a) a strong reduction of the paratropic currents in 5-MRs and (b) the fact that, due to the distortion, the paratropic currents point their effects in other directions.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/1058342
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