ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Drouin, Miller, Fry, Petkie, Helminger, Medvedev, J. Mol. Spectrosc. 236 (2006) 29 34Acknowledgment: The work was supported through the Ministry of Education, Youth and Sports of the Czech Republic (research program LC06071) and scholarship of the French government (Bourse du Gouvernement Francais Bourse de Doctorat en co-tutelle).

The ground state rotational spectrum of the near-spherical top molecule (SO2F2)-O-18 (sulfuryl fluoride) has been measured from 50 to 700 GHz. As for the parent isotopologue, (SO2F2)-O-16 [K. Sarka, J. Demaison, L Margules, I. Merke, N. Heineking, H. Burger, H. Ruland, J. Mol. Spectrosc. 200 (2000) 55-64], it was necessary to use a non-reduced Hamiltonian in order to obtain a satisfactory fit. It was possible to determine six quartic centrifugal distortion constants (instead of five for a standard asymmetric top) and five sextic constants (one of them not existing in the reduced Hamiltonian) could also be determined. This ground state level has also been analysed thanks to a tensorial formalism developed in Dijon. Only two tensorial sextic constants are fixed to zero, all others have been adjusted. Although (SO2F2)-O-18 is less spherical than (SO2F2)-O-16, the analysis was more difficult. It is partly due to the fact that (SO2F2)-O-18 is oblate whereas (SO2F2)-O-16 is prolate. The experimental quartic centrifugal distortion constants were found in good agreement with those calculated from the force field, confirming the correctness of the analysis. (C) 2009 Elsevier Inc. All rights reserved.

Author Institution: Optical Technology Division, NIST Gaithersburg, MD 20899, USA; Laboratoire Inter Universitaire des Systemes Atmospheriques,; CNRS, Universites Paris 12 et 7, 61 Av du General de Gaulle, 94010 Creteil; Cedex France; Anorg. Chemistry, University of Wuppertal, D-42119 Wuppertal, GERMANY

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Concern about the implication of chlorofluorocarbons (CFCs) in atmospheric ozone depletion has led to numerous measurements of the concentrations of halogen-containing compounds in the stratosphere. Of the various possible oxidation products of CFC's in the stratosphere, carbonyl chlorofluoride (COFCl) may receive special attention. High-resolution atmospheric infrared spectra are potential means of monitoring COFCl. However, there is little information on the spectroscopy of this molecule in the literature. We have therefore recorded spectra of pure 35Cl-enriched and natural samples of COFCl at ≤0.0033 cm−1 resolution with the BRUKER Fourier transform spectrometer at the University of Wuppertal. We present here the first high-resolution analysis of the six fundamental bands ν1 (CO stretching mode), ν2 (C–F stretching mode), ν3 (C–Cl stretching mode), ν4 (CFCl bending mode), ν5 (CFCl rocking mode), and ν6 (out of plane bending mode) located at 1875.8256, 1095.0646, 764.3876, 501.5941, 408.8099, and 666.5862 cm−1, respectively, for the COF35Cl isotopic species of carbonyl chlorofluoride. The ν3, ν4, ν5, and ν6 bands which are mainly of A-type, B-type, B-type, and C-type, respectively, appear as unperturbed. On the other hand, both the ν1 and ν2 bands have a hybrid character (with both A- and B-type transitions), and the analysis of these two bands was complicated by numerous resonances. Excellent results are obtained for the unperturbed ν3–ν6 bands and for the perturbed ν2 band, but for the ν1 band, the resonance scheme of which is more complex, the results of the analysis are slightly less satisfactory.

The tetracyanoborate anion is prepared for the first time as the tetrabutylammonium salt by the reaction of [NBu4]BX and BX3 (X = Br, Cl) in toluene with KCN. After purification and recrystallization of the product from CHCl3 colorless and needle size single crystals of [Bu4N][B(CN)(4)] are formed. After metathesis with AgNO3 the silver salt and subsequently with KBr the potassium salt is prepared. The three salts are characterized by single crystal X-ray diffraction (Ag[B(CN)(4)] P (4) over bar 3m, a = 5.732(1) Angstrom, V = 188.3 Angstrom(3), Z = 1, R-1 = 0.75%; K[B(CN)(4)] I4(1)/a. a = 6.976(1), c = 14.210(3) Angstrom, V = 691.5 Angstrom(3), Z = 4, R-1 = 1.90%; [Bu4N][B(CN)(4)] Pnna, a = 17.765(3), b = 11.650(2), c = 11.454(2) Angstrom, V = 2370.5 Angstrom(3), Z = 4, R-1 = 6.09%) and by NMR-, IR-, Raman- as well by UV-spectroscopy.