Structure, conformational properties and matrix photochemistry of S-(tert-butyl)trifluorothioacetate CF3C(O)SC(CH3)3

S-(tert-Butyl)trifluorothioacetate, CF3C(O)SC(CH3)3, was prepared by condensation of CF3C(O)Cl and (CH3)3CSH 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 spectr...

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Bibliographic Details
Published in:New journal of chemistry 2020-09, Vol.44 (34), p.14568-14577
Main Authors: Cayón, Vanina M, Erben, Mauricio F, Romano, Rosana M, Stammler, Hans-Georg, Mitzel, Norbert W, Della Védova, Carlos O
Format: Article
Language:English
Subjects:
Angles (geometry)
Approximation
Broadband
Charge density
Condensates
Crystal structure
Crystallization
Crystallography
Fourier transforms
Fractal geometry
Infrared spectroscopy
Mass spectrometry
Mathematical analysis
Molecular orbitals
NMR spectroscopy
Parameters
Photochemistry
Photolysis
Pressure curve
Quantum chemistry
Raman spectroscopy
Single crystals
Vapor phases
Vapor pressure
X-ray diffraction
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Summary:S-(tert-Butyl)trifluorothioacetate, CF3C(O)SC(CH3)3, was prepared by condensation of CF3C(O)Cl and (CH3)3CSH 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 by in situ crystallization reveals the presence of solely a synperiplanar conformation (syn form orientation of the C=O double bond with respect to the S–C single bond) belonging to the Cs point group of symmetry. Intermolecular C=O⋯C=O and C=O⋯H–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 at ca. 15 K was irradiated with UV-visible broadband light (200 ≤ λ ≤ 800 nm) and its photolysis products CF3SC(CH3)3 and CO were detected.
ISSN:1144-0546
1369-9261
DOI:10.1039/d0nj03173a