A comparative study of overtone CH-stretching vibrational circular dichroism spectra of fenchone and camphor

Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded for both enantiomers of camphor and fenchone using a home-built dispersive instrument. Two CH-stretching overtone regions and two CH-stretching/HCH-bending combination regions are investigated. The near-infrared VCD data are examined and compared with the corresponding previously published data of (3R)-(+)-methylcyclopentanone and (3R)-(+)-methylcyclohexanone. The absorption spectra of both the fundamental and overtone regions are also considered, and the fundamental CH-stretching VCD data are taken into account, where possible. An empirical assignment of the spectra is first considered, with special regard to the second CHstretching overtone region. This region is then investigated by a heuristic approach based on DFT calculations, using the hybrid functional B3LYP at the 6-31G** basis set level. Subsequently rotational strengths have been evaluated by use of a classical model based on the contribution of polarizable groups to the optical activity. The same models are also used to interpret the VCD spectra between 2000 and 3000 wavenumbers for (3R)-(+)-methylcyclopentanone-d(4).