Transmission of substituent effects through unsaturated systems Part 71. Influence of substituent on infrared and 13C NMR properties in rigid cisoid and transoid Conformations of α-enones

Serge Geribaldi, Yvonne Girault, P. Perjési, Jeanine Tortajada

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Dual substituent parameter (DSP) analysis is applied to model substituent effects on 13C substituent chemical shifts (SCS) and νCO stretching frequencies in two series of α-enones with rigid cisoïd and transoïd conformations. The regression coefficients of DSP analysis for the 13C SCS of the conjugated systems are discussed in terms of the relative importance of the various mechanisms of transmission of electronic effects. The differences between the regression coefficients relative to the field and resonance effects for the cisoïd and transoïd systems reflect very well the variations of geometries between both series. Concerning the i.r. data, the DSP analysis leads to an apparently unprecedented observation since it appears that the stretching frequencies of the carbonyl group are more sensitive towards substituent effect in the aplanar cisoïd system than in the more planar transoïd system. This surprising result is discussed.

Original languageEnglish
Pages (from-to)879-892
Number of pages14
JournalSpectrochimica Acta Part A: Molecular Spectroscopy
Volume48
Issue number6
DOIs
Publication statusPublished - 1992

Fingerprint

Chemical shift
Stretching
Conformations
Nuclear magnetic resonance
Infrared radiation
Geometry

ASJC Scopus subject areas

  • Engineering(all)

Cite this

@article{68ec13f4b5964c9ba2ef7c555dea0eeb,
title = "Transmission of substituent effects through unsaturated systems Part 71. Influence of substituent on infrared and 13C NMR properties in rigid cisoid and transoid Conformations of α-enones",
abstract = "Dual substituent parameter (DSP) analysis is applied to model substituent effects on 13C substituent chemical shifts (SCS) and νCO stretching frequencies in two series of α-enones with rigid ciso{\"i}d and transo{\"i}d conformations. The regression coefficients of DSP analysis for the 13C SCS of the conjugated systems are discussed in terms of the relative importance of the various mechanisms of transmission of electronic effects. The differences between the regression coefficients relative to the field and resonance effects for the ciso{\"i}d and transo{\"i}d systems reflect very well the variations of geometries between both series. Concerning the i.r. data, the DSP analysis leads to an apparently unprecedented observation since it appears that the stretching frequencies of the carbonyl group are more sensitive towards substituent effect in the aplanar ciso{\"i}d system than in the more planar transo{\"i}d system. This surprising result is discussed.",
author = "Serge Geribaldi and Yvonne Girault and P. Perj{\'e}si and Jeanine Tortajada",
year = "1992",
doi = "10.1016/0584-8539(92)80085-B",
language = "English",
volume = "48",
pages = "879--892",
journal = "Spectrochimica Acta - Part A Molecular Spectroscopy",
issn = "0584-8539",
publisher = "Pergamon Press Ltd.",
number = "6",

}

TY - JOUR

T1 - Transmission of substituent effects through unsaturated systems Part 71. Influence of substituent on infrared and 13C NMR properties in rigid cisoid and transoid Conformations of α-enones

AU - Geribaldi, Serge

AU - Girault, Yvonne

AU - Perjési, P.

AU - Tortajada, Jeanine

PY - 1992

Y1 - 1992

N2 - Dual substituent parameter (DSP) analysis is applied to model substituent effects on 13C substituent chemical shifts (SCS) and νCO stretching frequencies in two series of α-enones with rigid cisoïd and transoïd conformations. The regression coefficients of DSP analysis for the 13C SCS of the conjugated systems are discussed in terms of the relative importance of the various mechanisms of transmission of electronic effects. The differences between the regression coefficients relative to the field and resonance effects for the cisoïd and transoïd systems reflect very well the variations of geometries between both series. Concerning the i.r. data, the DSP analysis leads to an apparently unprecedented observation since it appears that the stretching frequencies of the carbonyl group are more sensitive towards substituent effect in the aplanar cisoïd system than in the more planar transoïd system. This surprising result is discussed.

AB - Dual substituent parameter (DSP) analysis is applied to model substituent effects on 13C substituent chemical shifts (SCS) and νCO stretching frequencies in two series of α-enones with rigid cisoïd and transoïd conformations. The regression coefficients of DSP analysis for the 13C SCS of the conjugated systems are discussed in terms of the relative importance of the various mechanisms of transmission of electronic effects. The differences between the regression coefficients relative to the field and resonance effects for the cisoïd and transoïd systems reflect very well the variations of geometries between both series. Concerning the i.r. data, the DSP analysis leads to an apparently unprecedented observation since it appears that the stretching frequencies of the carbonyl group are more sensitive towards substituent effect in the aplanar cisoïd system than in the more planar transoïd system. This surprising result is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0343948182&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0343948182&partnerID=8YFLogxK

U2 - 10.1016/0584-8539(92)80085-B

DO - 10.1016/0584-8539(92)80085-B

M3 - Article

AN - SCOPUS:0343948182

VL - 48

SP - 879

EP - 892

JO - Spectrochimica Acta - Part A Molecular Spectroscopy

JF - Spectrochimica Acta - Part A Molecular Spectroscopy

SN - 0584-8539

IS - 6

ER -