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(Trifluoromethyl)sulfanyl sulfinylimine, CF3SNSO. Structure and conformation in the electronic ground and excited states |
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| Authors: | R. M. Romano C. O. Della V dova H. -G. Mack H. Oberhammer |
| Affiliation: | a CEQUINOR (CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900), La Plata, Argentina b Laboratorio de Servicios a la Industria y al Sistema Cientifico (UNLP-CIC-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900), La Plata, Argentina c Institut für Physikalische und Theoretische Chemie, Universität Tübingen, Auf der Morgenstelle 8, D-72076, Tübingen, Germany |
| Abstract: | The molecular structure of (trifluoromethyl)sulfanyl sulfinylimine, CF3---S---N=S=O, was determined by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*, HF/6–31+G* and MP2/6–31+G*). Experimental and theoretical methods result in a structure with planar C---S---N=S=O skeleton (Cs symmetry), anti orientation of the S---C bond relative to the N=S bond and syn orientation of the S---N bond relative to the S=O double bond (anti-syn structure). The following skeletal parameters (ra values with 3σ uncertainties) were derived in the GED analysis: S---C, 1.831(4) Å; S---N, 1.684(5) Å; N=S, 1.538(6) Å; S=O, 1.453(6) Å; C---S---N, 94.6(8)°; S---N=S, 120.6(6)°; N=S=O: 116.5(8)°. A normal coordinate analysis based on FTIR (gas), FTIR (matrix) and Raman (liquid) spectra was performed. The UV (gas) spectrum was recorded and interpretation of the resonance Raman effect leads to the conclusion that the molecular symmetry (Cs) is retained upon electronic excitation. |
| Keywords: | (Trifluoromethylsulfanyl) sulfinylimine Electron diffraction Ab initio calculations Resonance Raman effect Vibrational spectra |
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