PUB - Publikationen an der Universität Bielefeld

S-(tert-Butyl)trifluorothioacetate, CF3C(O)SC(CH3)(3), was prepared by condensation of CF3C(O)Cl and (CH3)(3)CSH under vacuum conditions. The compound was isolated and properly characterized by using vibrational (infrared and Raman), UV-Vis and multinuclear NMR spectroscopy techniques and by mass spectrometry. The conformational preference and its crystal structure have been determined by means of FTIR spectroscopy (gas phase and Ar-matrix) and by X-ray diffraction. A charge density determination of X-ray diffraction (XRD) data of single crystals formed byin situcrystallization reveals the presence of solely a synperiplanar conformation (synform orientation of the C=O double bond with respect to the S-C single bond) belonging to theC(s)point group of symmetry. Intermolecular C=OMIDLINE HORIZONTAL ELLIPSISC=O and C=OMIDLINE HORIZONTAL ELLIPSISH-C interactions were detected in the crystal. Quantum-chemical calculations at the B3LYP/cc-pVTZ level of approximation reproduce the conformational preference and the experimental geometrical parameters fairly well. Vibrational information was obtained from Ar-matrix isolation FTIR and liquid Raman spectroscopy. Additionally, CF3C(O)SC(CH3)(3)isolated in solid Ar atca.15 K was irradiated with UV-visible broadband light (200 <= lambda <= 800 nm) and its photolysis products CF3SC(CH3)(3)and CO were detected.