TY - JOUR
T1 - 457. Molecular polarisability. Anisotropic polarisability of the cyanogroup from molar Kerr constants and dipole moments of eight nitriles
AU - Le Fèvre, R. J W
AU - Orr, B. J.
AU - Ritchie, G. L D
PY - 1965
Y1 - 1965
N2 - Molar Kerr constants and apparent dipole moments are recorded at 25° for acetonitrile, propionitrile, isobutyronitrile, t-butyl cyanide, chloroacetonitrile, trichloroacetonitrile, and benzonitrile, all in carbon tetrachloride, and for malononitrile in benzene. Inductive effects in these molecules are briefly discussed. Estimates of the anisotropic polarisability of the C-CN group in various environments are obtained. A regular increase of anisotropy is apparent for the C-CN group in the series MeCN, MeCH 2·CN, Me2CH·CN, Me3C·CN. The C-CN data from MeCN are satisfactorily applicable to Cl3C· CN, whilst, for ClCH2·CN, those from Me2CH· CN are most appropriate. The results for CH2(CN)2 anomalous, suggesting either bending of the C-CN group, exaltation effects, or solute-solvent interactions. The C-CN group polarisability in C 6H5·CN is much more anisotropic than in the aliphatic nitriles.
AB - Molar Kerr constants and apparent dipole moments are recorded at 25° for acetonitrile, propionitrile, isobutyronitrile, t-butyl cyanide, chloroacetonitrile, trichloroacetonitrile, and benzonitrile, all in carbon tetrachloride, and for malononitrile in benzene. Inductive effects in these molecules are briefly discussed. Estimates of the anisotropic polarisability of the C-CN group in various environments are obtained. A regular increase of anisotropy is apparent for the C-CN group in the series MeCN, MeCH 2·CN, Me2CH·CN, Me3C·CN. The C-CN data from MeCN are satisfactorily applicable to Cl3C· CN, whilst, for ClCH2·CN, those from Me2CH· CN are most appropriate. The results for CH2(CN)2 anomalous, suggesting either bending of the C-CN group, exaltation effects, or solute-solvent interactions. The C-CN group polarisability in C 6H5·CN is much more anisotropic than in the aliphatic nitriles.
UR - http://www.scopus.com/inward/record.url?scp=37049052588&partnerID=8YFLogxK
U2 - 10.1039/JR9650002499
DO - 10.1039/JR9650002499
M3 - Article
AN - SCOPUS:37049052588
SN - 0368-1769
SP - 2499
EP - 2505
JO - Journal of the Chemical Society (Resumed)
JF - Journal of the Chemical Society (Resumed)
ER -