Oxalyl halides

Hencher, J. Lawrence; King, G.W.

doi:10.1016/0022-2852(65)90095-0

Cited by 50 publications

(11 citation statements)

References 8 publications

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“…Subsequently it was synthesized in good yields from oxalyl chloride and NaF in polar aprotic solvents (2). From the first vibrational analysis, it was concluded that oxalyl fluoride is present in the planar trans form only (3). However, in two independent further vibrational studies (4,5), it was concluded that two rotamers are in an equilibrium in the gas phase: a more stable trans form and a less stable cis form.…”

Section: Introductionmentioning

confidence: 97%

“…The enthalpy difference was determined independently to be in the 2.3-4.4 kJ mol Ϫ1 range utilizing Raman spectroscopy (9). Despite many vibrational investigations during a period of more than 30 years (3)(4)(5)9), the vibrational fundamentals of trans and cis oxalyl fluoride are still not completely known and to our knowledge matrix studies on oxalyl fluoride with the aim of vibrational assignments are missing. The only matrix experiment on oxalyl fluoride was performed to study the interaction with molecular CsF (10).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational Spectra of cis and trans Oxalyl Fluoride and Their Site-Selective IR-Induced Rotamerization in an Argon Matrix

Sander

Willner

Khriachtchev

et al. 2000

Journal of Molecular Spectroscopy

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Vibrational Spectra of cis and trans Oxalyl Fluoride and Their Site-Selective IR-Induced Rotamerization in an Argon Matrix

Sander

Willner

Khriachtchev

et al. 2000

Journal of Molecular Spectroscopy

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“…Because no transitions of the second cis conformer were observed, King et al [6,9] concluded that (COF) 2 has a strictly trans configuration. However, Goubeau and Adelhelm and Durig et al [10][11][12][13], gathered vibrational spectra of (COF) 2 in the solid and the fluid phases.…”

Section: Introductionmentioning

confidence: 98%

“…In previous work, the vibrational [9] and vibronic [6] spectra were interpreted using only the trans (dOCCO = 180°, C 2h point symmetry) conformer. Because no transitions of the second cis conformer were observed, King et al [6,9] concluded that (COF) 2 has a strictly trans configuration.…”

Section: Introductionmentioning

confidence: 99%

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

Bokarev

Godunov

2010

Journal of Molecular Spectroscopy

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a b s t r a c tWe present a theoretical investigation of oxalyl fluoride (COF) 2 in the ground and the four lowest excited (two singlet and two triplet) electronic states of the n,p*-type mainly with the CASPT2(8-6)/cc-pVTZ method. Geometries, vibrational frequencies, potential energy functions of internal rotation, and adiabatic electronic transition energies were obtained. The conformer energy difference and the barrier to internal rotation in the ground electronic state were extrapolated to the complete basis set limit. The planar trans and cis conformations were the most stable configurations for all five electronic states under study. We found that the allowed electronic transition of the cis conformer has a transition energy that is significantly higher than that predicted in previous studies. For the excited states, the internal rotation was found to be accompanied by significant non-planar distortion of both carbonyl fragments, indicating strong coupling between these molecular motions.

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“…Early investigations of the vibrational spectra of oxalyl chloridefluoride (COCl-COF) [7,8] reported that at ambient temperature this molecule existed as only the trans conformer (dOCCO = 180°, C s symmetry, Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part V: Oxalyl chloridefluoride (COCl–COF)

2010

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The structure and conformational dynamics of the COCl-COF molecule in the ground and lowest excited electronic states were investigated theoretically by the CASPT2/cc-pVTZ method. The equilibrium geometric parameters, harmonic vibrational frequencies, potential functions of internal rotation, and adiabatic transition energies were obtained. According to the results of calculations, the molecule in the ground electronic state exist as the trans and gauche (dOCCO *30-40°) conformers with a low potential barrier to gauche-gauche transition therefore it is impossible to exclude existence of the cis conformer (instead of gauche) with a very broad and flat potential minimum. For all the investigated excited electronic states of oxalyl chloridefluoride molecule calculations predicted the trans and cis conformers. The strong coupling of internal rotation around the C-C bond and non-planar vibrations of carbonyl fragments was found for the excited electronic states. The results of calculation were utilized for reanalysis of experimentalÃ 1 A 00 X 1 A 0 andã 3 A 00 X 1 A 0 vibronic spectra reported in King (J Mol Spectrosc 50:209-219 (1974), and ibid. 48:592-599 (1973)). The vibrational assignment that does not contradict the vibrational spectroscopy data and results of calculations was obtained.

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Oxalyl halides

Cited by 50 publications

References 8 publications

Vibrational Spectra of cis and trans Oxalyl Fluoride and Their Site-Selective IR-Induced Rotamerization in an Argon Matrix

Vibrational Spectra of cis and trans Oxalyl Fluoride and Their Site-Selective IR-Induced Rotamerization in an Argon Matrix

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part V: Oxalyl chloridefluoride (COCl–COF)

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