Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН

Лаборатория изучения механизмов органических реакций

Ring current in arenonium ions. Hyperconjugation?

See responses to Henry Rzepa post.

About ring current in arenonium ions: V.A. Koptyug, Bulletin of the Academy of Sciences of the USSR, Division of chemical science May 1974, Volume 23, Issue 5, pp 1031-1045 DOI
"The transition of the protonated carbon atom to a hybridization state of the sp3 type should be accompanied by the substrate molecule losing its aromaticity. However, it is curious that evidently a high anisotropy of the magnetic susceptibility is retained for the protonated benzene ring, which is characteristic for aromatic systems and is usually explained by the induction of a ring pi-electron current in them."

"... The reasons for this phenomenon are not entirely clear. One of them is evidently the effective participation of the C-H bonds of the ring,"aliphatic" fragments of the benzenonium ions in the sigma,pi-conjugation with the charged pentadienyl portion of the ion, as a result of which a complete interruption of the ring conjugation chain fails to occur during protonation."

Replace CH2 with CMe2 in carbocation (IX) should decrease hyperconjugation.



Geometry optimization by DFT/PBE/L1 (PRIRODA program, basis aka cc-pVDZ)
Chemical shifts and NICS calculations by DFT/PBE/L22 (PRIRODA program, basis aka cc-pCVTZ)



There is no effect on anizotropy.

Click on links below to run java-applet jmol. Check "show chemical shifts" to see calculated shieldings and NICS.
IX   IX-Me