Structural studies of 1,1-dimethyl-2-oxy-1-silacyclohexane by means of matrix isolation infrared absorption spectroscopy.

Infrared spectra of gaseous, liquid, and matrix-isolated samples of newly synthesized 1,1-dimethyl-2-oxy-1-silacyclohexane were recorded. Raman spectra of 1,1-dimethyl-2-oxy-1-silacyclohexane in liquid and solid states were obtained in the temperature range from 170 to 340 K. Ab initio HF and DFT B3LYP calculations were performed in order to determine the possible conformations of 1,1-dimethyl-2-oxy-1-silacyclohexane and to make accurate assignment of the vibrational spectral bands. The study confirms the existence of only one chair-type conformer of 1,1-dimethyl-2-oxy-1-silacyclohexane.

Vibrational spectra, quantum chemical calculations and spectral assignments of 1,1-difluoro-1-silacyclohexane.

Raman spectra of 1,1-difluoro-1-silacyclohexane as a liquid, and as a solid at 78 K were recorded and depolarization data obtained. The infrared spectra of the vapour, liquid and amorphous and crystalline solids have been studied. In the low temperature IR and Raman spectra eight and three bands, respectively, were shifted a few cm(-1) when the sample crystallized. No bands vanished after crystallization in agreement with the assumption that only one conformer (chair) was present in all the states of aggregation. The compound exists in the stable chair conformation, whereas in the parent silacyclohexane a possible twist form should have more than 15 kJ mol(-1) higher energies than the chair, as derived from various calculations. The wavenumbers of the vibrational modes were calculated in the harmonic and anharmonic approximation employing B3LYP/cc-pVTZ calculations. The 27 A' and 21 A″ fundamentals were assigned on the basis of the calculations, infrared vapour contours, Raman depolarization measurements and infrared and Raman band intensities. An average, relative deviation of 1.5% was found between the observed and the anharmonic wavenumbers for the 48 modes.

NMR and Raman spectroscopy monitoring of proton/deuteron exchange in aqueous solutions of ionic liquids forming hydrogen bond: a role of anions, self-aggregation, and mesophase formation.

The H/D exchange process in the imidazolium-based room temperature ionic liquids (RTILs) 1-decyl-3-methyl-imidazolium bromide- and chloride ([C10mim][Br] and [C10mim][Cl]) in D2O solutions of various concentrations was studied applying (1)H, (13)C NMR, and Raman spectroscopy. The time dependencies of integral intensities in NMR spectra indicate that the H/D exchange in [C10mim][Br] at very high dilution (10(-4) mole fraction of RTIL) runs only slightly faster than in [C10mim][Cl]. The kinetics of this process drastically changes above critical aggregation concentration (CAC). The time required to reach the apparent reaction saturation regime in the solutions of 0.01 mole fraction of RTIL was less 10 h for [C10mim][Br], whereas no such features were seen for [C10mim][Cl] even tens of days after the sample was prepared. The H/D exchange was not observed in the liquid crystalline gel mesophase. The role of anions, self-aggregation (micellization), and mesophase formation has been discussed. Crucial influence of Br(-) and Cl(-) anions on the H/D exchange rates above CAC could be related to the short-range ordering and molecular microdynamics, in particular that of water molecules. The concept of the conformational changes coupled with the H/D exchange in imidazolium-based ionic liquids with longer hydrocarbon chains can be rejected in the light of (13)C NMR experiment. The revealed changes in (13)C NMR spectra are caused by the secondary ((13)C) isotope effects not being the signal shifts due to the conformational trans-gauche transition.

A high-resolution FT-IR study of the fundamental bands nu7, nu8, and nu18 of ethene secondary ozonide.

Ozonization reaction of ethene in neat film at 77 K was performed. Separation of ethene secondary ozonide from the other products of the reaction was performed by continuous pumping of the reactor. Only the products, which evaporated from the walls of the reactor at 185 K, were transferred to the gas cell. The high-resolution infrared absorption spectrum of gaseous ethene secondary ozonide (C(2)H(4)O(3)) in a static gas long-path absorption cell has been recorded in the 900-1100 cm(-1) spectral region at 185 K. The spectral resolution was 0.003 cm(-1). Analyses of the nu(7)(A) band at 1037.0 cm(-1), the nu(8)(A) band at 956.1 cm(-1), and the nu(18)(B) band at 1082.1 cm(-1) have been performed using the Watson Hamiltonian model (A, reduction; III(r), representation). A set of ground-state rotational and quartic centrifugal distortion constants have been obtained, and upper state spectroscopic constants have been determined for the bands investigated. A local resonance observed in nu(18) is explained as c-Coriolis interaction with nu(10) + nu(11).

Spectra and structure of silicon containing compounds. XXXIX. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propyltrifluorosilane.

The infrared (3100-40 cm(-1)) spectra of gaseous and solid and Raman (3200-20 cm(-1)) spectra of liquid with qualitative depolarization values and solid n-propyltrifluorosilane, CH(3)CH(2)CH(2)SiF(3), have been recorded. Additionally the infrared spectra of the sample in nitrogen and argon matrices have been recorded. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 135+/-14 cm(-1) (1.62+/-0.17 kJ mol(-1)) with the anti conformer the more stable form. At ambient temperature it is estimated that there is 51+/-2% of the gauche conformer present. Also the enthalpy difference in the liquid was obtained from variable temperature studies of the Raman spectra and from three conformer pairs an average value of 179+/-18 cm(-1) (2.14+/-0.22 kJ mol(-1)) was obtained again with the anti form the more stable conformer. Relatively complete vibrational assignments are proposed for both conformers based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios which are supported by normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities, depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d, p) and 6-311+G(2d, 2p) basis sets. By utilizing the previously reported microwave rotational constants for five isotopomers of CH(3)SiF(3) along with ab initio predicted structural values, r(0) parameters have been obtained for methyltrifluorosilane. Similarly, from the ab initio predicted parameters "adjusted r(0)" parameters have been estimated for both conformers of n-propyltrifluorosilane. The results are discussed and compared with those obtained for some similar molecules.