A molecule with small rotational constants containing an atom with a large nuclear quadrupole moment: The microwave spectrum of trans-1-iodoperfluoropropane

Dewberry, Christopher T.; Grubbs, Garry S.; Cooke, Stephen A.

doi:10.1016/j.jms.2009.06.008

Cited by 19 publications

(5 citation statements)

References 39 publications

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“…This work is consistent with previous studies , that have demonstrated that perfluoro-induced helicity of alkyl chains requires a chain length of at least four or five carbons.…”

Section: Discussionsupporting

confidence: 93%

“…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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“…This work is consistent with previous studies , that have demonstrated that perfluoro-induced helicity of alkyl chains requires a chain length of at least four or five carbons.…”

Section: Discussionsupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

et al. 2010

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“…In regards to objective (i) an m06-2X density functional was used [25,26], together with 6-311G** basis sets [27,28] obtained from the EMSL Basis Set Library [29,30]. This method has been shown to produce good quality rotational constants [11]. The calculated structure is given in Fig.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…Firstly, inspection of the F ¼ 3 2 energy sub-matrix shows a strong mixing between the J K À1 K þ1 ¼ 2 02 and 1 11 served before, see for example Ref. [39] and references therein, and are common in heavy iodine-containing compounds [11][12][13][14][15].…”

Section: Iodine Quadrupole Mediated Interstate Perturbationsmentioning

confidence: 99%