The structures of the trifluoromethyl halides

Bowen, H. J. M.

doi:10.1039/tf9545000444

Cited by 24 publications

(6 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This contradicted earlier finding of Bertan et al 48 who performed theoretical analysis for the CF 3 Cl system in vacuo and in solution at the MP2 level with the 4-31G* basis set. Also in this work, the solvent was modeled as dielectric continuum described by dielectric constant ε = 37 and introduced directly into the quantum calculations.…”

Section: Introductioncontrasting

confidence: 80%

“…One electron attachment to the CF 3 X (X = Cl, Br, I) molecules are very important reactions, which were explored in many experimental − and theoretical works. − In our very recent theoretical studies, we studied in detail the most important properties of substrates and products of the one electron reduction of CF 3 X (X = Cl, Br, I) molecules in vacuo. According to this work, and also in agreement with some earlier studies, these processes proceed via formation of the locally stabilized radical anions CF 3 X¯, which further dissociate to the radical CF 3 • and halide anions X¯.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ignaczak

2012

J. Phys. Chem. A

View full text Add to dashboard Cite

In this article, an effect of solvent on potential energy surfaces, constructed at the PBE1PBE/aug-cc-pVTZ level vs C-X distances for the neutral molecules CF(3)X (X = Cl, Br, I) and the corresponding radical anions CF(3)X¯, is studied using the polarizable continuum model (PCM). The properties and energy changes in these compounds in the presence of argon, acetonitrile (ACN), and dimethyl sulfoxide (DMSO) are compared to the results obtained earlier in vacuo. The presence of solvent very weakly influences the neutral molecules, but it significantly changes properties of radical anions, such as structural parameters and partial charges on atoms. The effect of solvent is manifested also in strong modification of the potential energy surfaces, on which the minima corresponding to the locally stabilized forms of CF(3)X¯ are shallower in argon, and in ACN and DMSO, they almost disappear. This in turn results in much higher energy barriers (by about 0.2-0.3 eV) for the reductive cleavage of C-X bonds in polar solvents than in vacuo. Despite different dielectric constants of ACN and DMSO, the potential energy surfaces obtained in these two solvents are very similar, and the activation energies equal, respectively, 0.635 and 0.637 eV for CF(3)Cl; 0.479 and 0.481 eV for CF(3)Br; and 0.336 and 0.337 eV for CF(3)I.

show abstract

Section: Introductioncontrasting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ignaczak

2012

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…(34]. Anderson [35) and Bowen [36] have reported the structural parameters from their electron diffraction measurements. We have adopted the values obtained from microwave measurements [33], which are given in table 3. The infrared and Raman measurements have been reported by many workers [22,24,[37][38][39][40][41][42] and their assignments are in very good agreement.…”

Section: Chlorodibromomethane' (Chcibr2)mentioning

confidence: 99%

Ideal gas thermodynamic properties of CH4−(a+b+c+d)FaClbBrcId Halomethanes

Kudchadker

1978

Journal of Physical and Chemical Reference Data

View full text Add to dashboard Cite

Densities of liquid CH4−a X a (X=Br,I) and CH4−(a+b+c+d)F a CI b Br c I d halomethanesThe availa,ble molecular parameters, fundamental frequencies, and enthalpies of formation at 298.15K (llHr(298}) for halomethanes of the type CH4-(a+b+c+dlFaClr,BrcId have been critically evaluated and recommended values selected. Molecular parameters and llHfO(298) for some halomethanes have been estimated as the experimental values for these compounds are not available. This information has been utilized to calculate the ideal gas thermodynamic properties C;, So, HO-H~,-(Go-H~)/T, llHr, ;lOr, and logKf from o to 1500 K and at a pressure of one atmosphere using the rigid rotor-harmonic oscillator approximation for the following compounds: CHzFBr, T~h h~ If the values for angle YCY in CY:;:W2 ano {l.ngle ZCZ in CZ 2 W2 are available, then LYCZ= 1j2( LYCY + LZCZ). (2) Bond angle XCZ: Very few. values are available for LXCZ in halomethanes having two X atoms. Hence values of LXCZ angles

show abstract

“…The structure oftetrafluorometh:mp (~:nh()n tAt.rafluoride) has been studied by Alcock and Hurst (1951), using neutron diffraction; and by Bowen (1954), Thornton (1954. Hoffman and Livingston (1953), and Brockway (1954), using the electron diffraction technique.…”

Section: Tetrafluoromethanementioning

confidence: 99%

Ideal Gas Thermodynamic Properties of Eight Chloro- and Fluoromethanes

Rodgers

Chao

Wilhoit

et al. 1974

Journal of Physical and Chemical Reference Data

View full text Add to dashboard Cite

The structural data, vibrational assignments, enthalpies of vaporization and formation for chloromethane, dichloromethane, trichloromethane, tetrachloromethane, fluoromethane, difluoromethane, trifluoromethane, and tetrafluoromethane were critically reviewed_ Based on the selected best values, the thermodynamic properties for each of these eight chloro-and fluoromethanes were calculated by statistical thermodynamic methods using the rigid-rotor harmonic-oscillator approximations. The derived entropies and heat capacities are compared with the available third law entropies and vapor heat capacities. The calculated values of C~, So, and l:!.Hr at 298.15 and 700 K are compared with those reported in the other major compilations.

show abstract

The structures of the trifluoromethyl halides

Cited by 24 publications

References 1 publication

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ideal gas thermodynamic properties of CH4−(a+b+c+d)FaClbBrcId Halomethanes

Ideal Gas Thermodynamic Properties of Eight Chloro- and Fluoromethanes

Contact Info

Product

Resources

About

The structures of the trifluoromethyl halides

Cited by 24 publications

References 1 publication

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF3X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF3X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ideal gas thermodynamic properties of CH4−(a+b+c+d)FaClbBrcId Halomethanes

Ideal Gas Thermodynamic Properties of Eight Chloro- and Fluoromethanes

Contact Info

Product

Resources

About

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study