New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry

Tamone, Luciana M.; Picone, Andrea; Romano, Rosana M.

doi:10.1016/j.jpap.2021.100019

Cited by 3 publications

(3 citation statements)

References 24 publications

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“…Gas Electron Diffraction (GED) measurements revealed that the syn-anti rotamer predominates at ambient temperature, comprising 67(8)% of the gas-phase composition, whereas matrix-FTIR estimated its presence at 59(5)% [6]. Similar results were obtained for ClC(O)OSO2CF3, with the syn-anti conformer constituting 66(8)% according to matrix-FTIR measurements [7] and 67 (11) % based on GED experiments [8]. Notably, FC(O)OSO2CF3 and ClC(O)OSO2CF3 are unique in exhibiting prevailing anti conformation around the S−O single bond, unlike other XOSO2CF3 species, which typically adopt Disclaimer/Publisher's Note: The statements, opinions, and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s).…”

Section: Introductionsupporting

confidence: 59%

Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation

Spaltro,

Peluas,

Della Védova

et al. 2024

Preprint

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The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through vibrational experimental methods (gas-phase FTIR, liquid-phase Raman, and Ar-matrix FTIR spectroscopy) and Density Functional Theory (DFT) calculations. A potential energy surface was computed using the B3P86 /6-31+g(d) approximation as a function of the dihedral angles τ1 = CCOS and τ2 = COSC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp and cc-pvtz). The global minimum corresponds to a syn-anti conformer (the CO double bound syn with respect the O−S single bond and the C−O single bond anti with respect to de S−C single bond). The other two minima represent enantiomeric syn-gauche forms. The Ar-matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broad-band UV-visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar-matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperatures was composed of approximately 60-70% of the syn-anti conformer and 30-40% of the syn-gauche form.

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Section: Introductionsupporting

confidence: 59%

Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation

Spaltro,

Peluas,

Della Védova

et al. 2024

Preprint

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“…Gas electron diffraction (GED) measurements revealed that the syn-anti rotamer predominates at ambient temperature, comprising 67(8)% of the gas-phase composition, whereas matrix FTIR estimated its presence at 59(5)% [6]. Similar results were obtained for ClC(O)OSO 2 CF 3 , with the syn-anti conformer constituting 66(8)% according to matrix FTIR measurements [7] and 67 (11)% based on GED experiments [8]. Notably, FC(O)OSO 2 CF 3 and ClC(O)OSO 2 CF 3 are unique in exhibiting a prevailing anti conformation around the S−O single bond, unlike other XOSO 2 CF 3 species, which typically adopt a gauche conformation (see Refs.…”

Section: Introductionsupporting

confidence: 58%

“…This process has been observed for several other molecules (see, for example, Refs. [11][12][13], and references cited therein). This behaviour constitutes a very important tool for a clear assignment of the IR absorptions to each conformer.…”

Section: Introductionmentioning

confidence: 99%

Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation

Spaltro,

Peluas,

Della Védova

et al. 2024

Spectroscopy Journal

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The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.

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Light induced reactions in cryogenic matrices (highlights 2021–2022)

Fausto,

Nikitin,

Nogueira

2023

Photochemistry

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This chapter surveys research on light induced reactions of organic molecules investigated in cryogenic matrices that has been reported during 2021 and 2022. It highlights studies dealing with conformational changes, tautomerizations and other structural isomerizations induced either by ultraviolet/visible or infrared light, as well as photofragmentation reactions. Emphasis is given to reactive intermediates, including nitrenes, carbenes and radicals. The studies featured in the present review are examples of recent applications of the matrix isolation method, coupled with spectroscopic probing, to these areas of investigation.

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New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry

Cited by 3 publications

References 24 publications

Conformational Analysis of Trifluoroacetyl Triflate, CF<sub>3</sub>C(O)OSO<sub>2</sub>CF<sub>3</sub>: Experimental Vibrational and DFT Investigation

Conformational Analysis of Trifluoroacetyl Triflate, CF<sub>3</sub>C(O)OSO<sub>2</sub>CF<sub>3</sub>: Experimental Vibrational and DFT Investigation

Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation

Light induced reactions in cryogenic matrices (highlights 2021–2022)

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