INVESTIGADORES
DELLA VEDOVA Carlos Omar
artículos
Título:
Structure, conformational properties and matrix photochemistry of S -( tert -butyl)trifluorothioacetate CF 3 C(O)SC(CH 3 ) 3
Autor/es:
CAYÓN, VANINA M.; ERBEN, MAURICIO F.; ROMANO, ROSANA M.; STAMMLER, HANS-GEORG; MITZEL, NORBERT W.; DELLA VÉDOVA, CARLOS O.
Revista:
NEW JOURNAL OF CHEMISTRY
Editorial:
ROYAL SOC CHEMISTRY
Referencias:
Lugar: CAMBRIDGE; Año: 2020 vol. 44 p. 14568 - 14577
ISSN:
1144-0546
Resumen:
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[double bond, length as m-dash]O double bond with respect to the S?C single bond) belonging to the Cs point group of symmetry. Intermolecular C[double bond, length as m-dash]O⋯C[double bond, length as m-dash]O and C[double bond, length as m-dash]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.