DFT and ab initio theoretical study for the CF3S+CO reaction

Pan, Ya‐Ru; Tang, Yizhen; Wang, Rongshun

doi:10.1016/j.jfluchem.2010.10.005

Cited by 4 publications

(2 citation statements)

References 33 publications

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“…Therefore, the existence of a + CX double bond or even a triple bond as in the diatomic + CX is more than questionable. Knowledge of the CX bonding mechanism is desirable in many areas of chemistry ranging from synthesis, thermochemistry, spectroscopy, ,, reaction mechanism, and reaction dynamics ,− to fields such as astrochemistry …”

Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of the Multiplicity of Carbon–Halogen Bonds: Carbenium and Halonium Ions with F, Cl, Br, and I

2014

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CX (X = F, Cl, Br, I) and CE bonding (E = O, S, Se, Te) was investigated for a test set of 168 molecules using the local CX and CE stretching force constants k(a) calculated at the M06-2X/cc-pVTZ level of theory. The stretching force constants were used to derive a relative bond strength order (RBSO) parameter n. As alternative bond strength descriptors, bond dissociation energies (BDE) were calculated at the G3 level or at the two-component NESC (normalized elimination of the small component)/CCSD(T) level of theory for molecules with X = Br, I or E = Se, Te. RBSO values reveal that both bond lengths and BDE values are less useful when a quantification of the bond strength is needed. CX double bonds can be realized for Br- or I-substituted carbenium ions where as suitable reference the double bond of the corresponding formaldehyde homologue is used. A triple bond cannot be realized in this way as the diatomic CX(+) ions with a limited π-donor capacity for X are just double-bonded. The stability of halonium ions increases with the atomic number of X, which is reflected by a strengthening of the fractional (electron-deficient) CX bonds. An additional stability increase of up to 25 kcal/mol (X = I) is obtained when the X(+) ion can form a bridged halonium ion with ethene such that a more efficient 2-electron-3-center bonding situation is created.

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Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of the Multiplicity of Carbon–Halogen Bonds: Carbenium and Halonium Ions with F, Cl, Br, and I

2014

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“…Local modes are perfectly suited to describe the strength of CX bonds in a quantitative rather than just qualitative way. The information gained in this way provides an important insight into the structure, stability, and reactivity of CX containing compounds, which are relevant in many areas of chemistry ranging from synthesis, spectroscopy, reaction mechanism, and reaction dynamics to astrochemistry …”

Section: Introductionmentioning

confidence: 99%

Are carbon—halogen double and triple bonds possible?

Kalescky

Kraka

Cremer

2014

Int J of Quantum Chemistry

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The carbonAhalogen and carbonAchalcogen bonding of 84 molecules was investigated utilizing local vibrational modes calculated at the M06-2X/cc-pVTZ level of theory including anharmonicity corrections in all cases. The relative bond strength order of each CX or CE bond (X 5 F, Cl; E 5 O, S) was derived from the local CX or CE stretching force constant and compared with trends of calculated bond lengths r and bond dissociation energies (BDE) obtained at the G3 level of theory. It is shown that both bond length r and BDE are not reliable bond strength descriptors. The CX double bond is realized for some Cl-substituted carbenium ions, however, not for the cor-responding F-derivatives. Diatomic CF 1 and CCl 1 possess fully developed double bonds but not, as suggested in the literature, triple bonds. Halonium ions have fractional (electron-deficient) CX bonds, which can be stabilized by r-donor substituents or by an increased polarizability of the halogen atom as with Cl. Bridged halonium ions are more stable than their acyclic counterparts, which results from more effective two-electron-three-center bonding.

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A computational study on the reaction mechanism of C2H5S with HO2

Zhang

et al. 2012

Computational and Theoretical Chemistry

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DFT and ab initio theoretical study for the CF3S+CO reaction

Cited by 4 publications

References 33 publications

Quantitative Assessment of the Multiplicity of Carbon–Halogen Bonds: Carbenium and Halonium Ions with F, Cl, Br, and I

Quantitative Assessment of the Multiplicity of Carbon–Halogen Bonds: Carbenium and Halonium Ions with F, Cl, Br, and I

Are carbon—halogen double and triple bonds possible?

A computational study on the reaction mechanism of C2H5S with HO2

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