The gas phase characterization of perfluorobutyryl chloride, C3F7COCl, using chirped pulse Fourier transform microwave spectroscopy

Grubbs, Garry S.; Cooke, Stephen A.

doi:10.1016/j.cplett.2009.10.043

Cited by 7 publications

(6 citation statements)

References 23 publications

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“…The values of the determined parameters are given in Table 6. The value of F seems very reasonable at 160 (7) GHz. The error on the V 3 value is likely considerably larger than stated given that other rotational constants were held fixed.…”

Section: Experimental Results and Analysesmentioning

confidence: 67%

“…Perfluorination is the act of completely replacing all hydrogen atoms in a molecular system by fluorine atoms. Curiosity surrounds the numerous effects of perfluorination on (i) hydrocarbons − and (ii) functionalized hydrocarbons. − The structural effects of perfluorination include (i) differing lowest energy conformations and (ii) reduced conformational flexibility of perfluorinated compounds compared to the hydrogenated analogues. This is pertinent in regards to rationalizing the so-called “perfluoroalkyl effect” which is believed to be steric in origin and concerns the kinetic and thermodynamic stabilizing effect that fluorination imparts to a carbon skeleton .…”

Section: Introductionmentioning

confidence: 99%

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Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

et al. 2010

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Propionyl chloride and perfluoropropionyl chloride have been characterized using chirped pulse Fourier transform microwave spectroscopy between the frequency range of 8 and 14 GHz. Molecules were studied in separate experiments in supersonic expansions of argon. The (35)Cl, (37)Cl, and each of the monoisotopic (13)C substituted isotopologues of propionyl chloride were observed. The (35)Cl and (37)Cl isotopologues of perfluoropropionyl chloride were observed. Analyses of the resulting microwave spectra have yielded spectroscopic constants for the target molecules. The analyses indicate that, under the conditions of these experiments, both molecules are only detectable as cis conformers in which angleCCCO = 0 degrees . Comparisons are made between the electronic and geometric structure of propionyl chloride and perfluoropropionyl chloride, and also other acyl chlorides. The data produced are relevant in regards to quantifying the known destabilizing effect of perfluoroalky chains on carbonyl groups. Distinct differences in electronegativity between the CH(3)CH(2)CO- and CF(3)CF(2)CO- groups are discussed. Methyl group internal rotation is observed for propionyl chloride and has been analyzed to produce a V(3) barrier height.

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Section: Experimental Results and Analysesmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

et al. 2010

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“…Grubbs II et al . reported the molecular structure of perfluorobutanoyl chloride by using microwave spectroscopy and quantum chemical calculations.…”

Section: Resultsmentioning

confidence: 99%

“…15 Thus, 6 ml (49 mmol) of perfluorobutanoic acid, CF 3 CF 2 CF 2 C(O)OH, was slowly added using a dropping funnel attached to a twin-neck round bottom flask containing 12.50 g (60 mmol) of PCl 5 . Two "U" shaped traps immersed in cool baths (-50 °C and -80 °C, respectively) were connected to the condenser and a CaCl 2 trap was 6 microwave spectroscopy. Thus, the potential energy curve around the τ(CC-CCl) dihedral angle has been computed with the MP2/cc-pVTZ, B3LYP/cc-pVTZ and B3LYP/6-311+g(d) level of approximations ( Figure 1).…”

Section: Synthesismentioning

confidence: 99%

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Photoexcitation, Photoionization, and Photofragmentantion of CF₃CF₂CF₂C(O)Cl Using Synchrotron Radiation between 13 and 720 eV

et al. 2015

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The main inner shell ionization edges of gaseous CF3CF2CF2C(O)Cl, including Cl 2p, C 1s, O 1s, and F 1s, have been measured in Total Ion Yield (TIY) mode by using tunable synchrotron radiation, and several resonance transitions have been assigned with the help of quantum chemical calculations. Interestingly, resonance transitions observed in the C 1s region can be assigned to different carbon atoms in the molecule according to the degree of fluorine substitution. Ionic photofragmentation processes have been studied by time-of-flight mass spectrometry in the Photoelectron-Photoion-Coincidence (PEPICO) and Photoelectron-Photoion-Photoion-Coincidence (PEPIPICO) modes. These techniques revealed a "memory-lost" effect especially around the C 1s region, since the fragmentation events are independent of the energy range considered. Moreover, different fragmentation mechanisms were inferred from these spectra in the valence (13.0-21.0 eV) as well as in the inner (180.0-750.0 eV) electronic energy regions. The vibrational spectral features of CF3CF2CF2C(O)Cl have been interpreted in terms of a conformational equilibrium between two conformations (gauche and anti of the CC single bond with respect to the CCl one) at room temperature, as determined from quantum chemical calculations and the detailed analysis of the infrared spectrum.

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A conformational study of butyryl chloride using chirped pulse Fourier transform microwave spectroscopy and quantum chemical calculations

Powoski¹,

Grubbs²,

Cooke³

2010

Journal of Molecular Structure

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The gas phase characterization of perfluorobutyryl chloride, C3F7COCl, using chirped pulse Fourier transform microwave spectroscopy

Cited by 7 publications

References 23 publications

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

Photoexcitation, Photoionization, and Photofragmentantion of CF₃CF₂CF₂C(O)Cl Using Synchrotron Radiation between 13 and 720 eV

A conformational study of butyryl chloride using chirped pulse Fourier transform microwave spectroscopy and quantum chemical calculations

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The gas phase characterization of perfluorobutyryl chloride, C3F7COCl, using chirped pulse Fourier transform microwave spectroscopy

Cited by 7 publications

References 23 publications

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

Photoexcitation, Photoionization, and Photofragmentantion of CF3CF2CF2C(O)Cl Using Synchrotron Radiation between 13 and 720 eV

A conformational study of butyryl chloride using chirped pulse Fourier transform microwave spectroscopy and quantum chemical calculations

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Photoexcitation, Photoionization, and Photofragmentantion of CF₃CF₂CF₂C(O)Cl Using Synchrotron Radiation between 13 and 720 eV