The infrared and Raman spectra of oxalyl bromide

Kidd, K.G.; King, G.W.

doi:10.1016/0022-2852(68)90084-2

Cited by 18 publications

(2 citation statements)

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“…On the other hand, halogenated carbonyls such as oxalyl dibromide (BrC(O)C(O)Br) and oxalyl dichloride (ClC(O)C(O)Cl) are utilized widely as reagents in organic reactions, which have been characterized [43][44][45][46]. In the atmosphere, the sources [47,48] of oxalyl dibromide (BrC(O)C(O)Br) and oxalyl dichloride (ClC(O)C(O)Cl) are the OH-initiated oxidation of 1,2-dibromoethane and C 2 Cl 4 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Long

Wang

et al. 2011

Int J of Quantum Chemistry

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ABSTRACT:The initial reactions of HO 2 with oxalyl dichloride, oxalyl dibromide, acetyl chloride, and acetyl bromide are studied for the first time using the density functional theory with CAM-B3LYP and wB97XD, CBS-QB3, and G3 theoretical methods and the transition state theory. The reactions occur via the similar mechanism that the prereactive complex is formed before the transition state and product. The calculated results demonstrate that the HO 2 radical with ClC(O)C(O)Cl and BrC(O)C(O)Br reactions is feasible and could play a significant role in the atmosphere because the barriers are 0.13 kcal/mol, À0.05 kcal/mol with respect to the free reactants, respectively at the CBS-QB3 level of theory. In addition, the rate constants of the HO 2 þ ClC(O)C(O)Cl and HO 2 þ BrC(O)C(O)Br reactions are computed to be 1.37 Â 10 À15 cm 3 mol À1 s À1 , 1.70 Â 10 À15 cm 3 mol À1 s À1 at 298 K. However, the HO 2 reactions with acetyl chloride and acetyl bromide are of no importance because of higher activated barrier and slower rate constant.

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Section: Introductionmentioning

confidence: 99%

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Long

Wang

et al. 2011

Int J of Quantum Chemistry

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“…It was known over four decades ago that the molecules of oxalyl chloride (OXCL) and oxalyl bromide (OXBR) have a centrosymmetric trans form in the crystal . Some analyses of the IR and Raman spectra of OXCL and OXBR, , and their homologues oxalyl fluoride (OXF) and oxalyl chloride fluoride (OXCLF), led to the conclusion that this form was likely the only one present in the liquid and gas phases as well. However, other IR and Raman studies of these substances (OXCL, OXBR, OXF, , OXCLF) suggested that, in addition to the expected planar trans form, a second conformer, universally assumed to be the planar cis form of C 2 v symmetry, was also present in the fluid phases.…”

Section: Introductionmentioning

confidence: 99%

Conformational Analysis. 24. Structure and Composition of Gaseous Oxalyl Fluoride, C₂F₂O₂: Electron-Diffraction Investigation Augmented by Data from Microwave Spectroscopy and Molecular Orbital Calculations

et al. 2006

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The molecular structure and composition of gaseous oxalyl fluoride (OXF) has been investigated by electron diffraction (GED) at nozzle-tip temperatures of -10, 149, and 219 degrees C. The GED data were augmented by molecular orbital calculations, and the analysis was aided by use of rotational constants from microwave (MW) spectroscopy. As in the other oxalyl halides, there are two stable species, of which the more stable is periplanar anti (i.e., trans). However, unlike these other halides in which the second form is gauche, the second form of oxalyl fluoride was known from MW work to be periplanar syn (i.e., cis). Our results are consistent with a mixture of trans and cis forms, and yield values for the structural parameters, the composition of the system at the three temperatures cited, and the thermodynamic quantities deltaG(o), deltaH(o), and deltaS(o) for the reaction trans --> cis. Some trans/cis distances (r(g)/Angstrom) and angles (<(alpha)/deg) at -10 degrees C are r(C=O) = 1.178(2)/1.176(2), r(C-F) = 1.323(2)/1.328(2); r(C-C) = 1.533(3)/1.535(3), <(C-C=O) = 126.4(2)/124.2(2), <(C-C-F) = 109.8(2)/112.2(2), and <(O-C-F) = 123.8(2)/123.6(2). The mixture compositions (percent trans) at -10 degrees C/149 degrees C/219 degrees C are 75(3)/58(7)/52(8), from which deltaH(o) and deltaSO) are found to be 1.14 kcal/mol and 2.12 cal/(mol x deg). The system properties are discussed.

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Detection, determination and characterization

Weiler‐Feilchenfeld

1972

PATAI'S Chemistry of Functional Groups

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The infrared and Raman spectra of oxalyl bromide

Cited by 18 publications

References 4 publications

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Conformational Analysis. 24. Structure and Composition of Gaseous Oxalyl Fluoride, C₂F₂O₂: Electron-Diffraction Investigation Augmented by Data from Microwave Spectroscopy and Molecular Orbital Calculations

Detection, determination and characterization

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The infrared and Raman spectra of oxalyl bromide

Cited by 18 publications

References 4 publications

Theoretical study on HO2‐initiated atmospheric oxidation of halogenated carbonyls

Theoretical study on HO2‐initiated atmospheric oxidation of halogenated carbonyls

Conformational Analysis. 24. Structure and Composition of Gaseous Oxalyl Fluoride, C2F2O2: Electron-Diffraction Investigation Augmented by Data from Microwave Spectroscopy and Molecular Orbital Calculations

Detection, determination and characterization

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Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Theoretical study on HO₂‐initiated atmospheric oxidation of halogenated carbonyls

Conformational Analysis. 24. Structure and Composition of Gaseous Oxalyl Fluoride, C₂F₂O₂: Electron-Diffraction Investigation Augmented by Data from Microwave Spectroscopy and Molecular Orbital Calculations