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Isomerie Rotationnelle du Formiate de Tertiobutyle: Etude par Spectrometrie de Vibration de I'Influence des Solvants et des Cations
Author(s) -
Omura Yoko,
Corset Jacques,
Moravie Rose Marie
Publication year - 1981
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250110104
Subject(s) - chemistry , raman spectroscopy , solvation , polar , infrared spectroscopy , ternary operation , solvation shell , formate , crystallography , molecule , infrared , stereochemistry , organic chemistry , physics , astronomy , computer science , optics , catalysis , programming language
Raman spectra of t t‐butyl formate HCOOC(CH 3 ) 3 were recorded in various solvents in the ν(CO) region and below 1000 cm −1 where appear the bands sensitive to the conformation. It is shown that, compared to the pure liquid, the cis‐trans equilibrium is shifted towards the trans , the more polar form, in polar solvents and towards the cis form in non‐polar solvents. For binary solutions HCOOC(CH 3 ) 3 ‐Ba(ClO 4 ) z and ternary solutions HCOOC(CH 3 ) 3 ‐Ba(ClO 4 ) 2 ‐CH 3 CN, the infrared and Raman spectra, recorded in the same regions, show that the complexation of the ester carbonyl group by the Ba 2+ cations favours the trans conformation as do the polar solvents. Through spectral analysis of the concentrated Ba(ClO 4 ) 2 ester solution and of the solvation number it is shown that the Ba 2+ cation is octahedrally surrounded by the carbonyl groups of six molecules in its first solvation shell.