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Conformational equilibria in dihaloheptasilanes X 2 Si[SiMe(SiMe 3 ) 2 ] 2 with X = F, Cl, Br, I: A Raman spectroscopic and quantum chemical DFT study
Author(s) -
Dzambaski A.,
Flock M.,
Hassler K.
Publication year - 2007
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.1755
Subject(s) - conformational isomerism , raman spectroscopy , chemistry , quantum chemical , wavenumber , crystallography , analytical chemistry (journal) , spectroscopy , molecule , physics , organic chemistry , quantum mechanics , optics
Equilibrium geometries, stabilities and vibrational wavenumbers for conformers of the dihaloheptasilanes X 2 Si[SiMe(SiMe 3 ) 2 ] 2 with X = F, Cl, Br and I were calculated at the density functional B3LYP level employing 6‐311G(d) basis sets and SDD pseudopotentials for Br and I. Two spectroscopically distinct low‐energy conformers were located for all four heptasilanes with energy differences of 5.5, 4.7, 1.9 and 1.2 kJ mol −1 for X = F, Cl, Br and I, respectively. Five more conformers were found for difluoroheptasilane and four for X = Cl, Br and I. They all have relative energies larger than 7.5 and up to 17 kJ mol −1 and are negligibly populated at room temperature. Variable temperature solution Raman spectra (−70 to + 100 °C) in a wavenumber range typical for SiSi stretching vibrations (280‐350 cm −1 ) confirm these results. For X = Br and I, no temperature effects at all could be observed as a very rapid inter‐conversion between the two low‐energy conformers, which is fast even on the time scale of Raman spectroscopy, occurs. For X = Cl, rapid inter‐conversion also occurs, and a third conformer could be detected at higher temperatures (50–100 °C). For X = F, intensity changes with temperature are consistent with the presence of two low‐energy conformers. Copyright © 2007 John Wiley & Sons, Ltd.