Dissociation dynamics of acetyl chloride and cis-trans isomerisation of methoxychloro carbene and chlorohydroxymetyl carbene

Sumathi, R.; Chandra, Asit K.

doi:10.1016/0301-0104(94)85016-x

Cited by 19 publications

(38 citation statements)

References 42 publications

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“…This led to the assumption of a ' tighter ' TS for HX elimination reactions as opposed to the ' looser ' TS predicted by ab initio calculations. [6][7][8]15,18 Our results, with that of the extensive calculations reported by McGrath and Rowland 18 suggest that experimental Arrhenius parameters need not reveal the intricacies of the TS structure. However, these parameters will remain valuable for modeling in practical situations such as combustion, incineration, detonation, etc..…”

Section: Iii2d Hf and Hci Elimination Reaction From Cfesupporting

confidence: 63%

“…The HX elimination reactions from haloethanes have continued to attract both experimental [1][2][3][4][5][6] and theoretical efforts. [6][7][8][9][10] One of the main reasons for this interest is the fact that these reactions offer an excellent example for a truly unimolecular reaction involving complicated motions along at least 4 bonds. It is ideal for discussing the intricacies of ' the reaction coordinate ' in a classroom.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

Rajakumar

Arunan

2003

Phys. Chem. Chem. Phys.

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Section: Iii2d Hf and Hci Elimination Reaction From Cfesupporting

confidence: 63%

Section: Introductionmentioning

confidence: 99%

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

Rajakumar

Arunan

2003

Phys. Chem. Chem. Phys.

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“…Although mechanisms II and III below initially appear plausible, the experimental results do not support initial dissociation of the C−Cl bond that is required by these mechanisms Furthermore, the experimental results do not support a mechanism involving an intermediary triplet state as described by mechanism IV: The evidence supporting mechanism I includes the singular primary reaction products, the highly favored elimination reaction path calculated for the ground electronic state, the observed alignment of the reaction products, and the strong similarities between the determined structure of the HCl·ketene complexes and the calculated transition-state structure …”

Section: Discussionmentioning

confidence: 69%

“…Recently, Sumathi and Chandra explored the potential energy surface of acetyl chloride in the electronic ground and lowest adiabatic triplet states using ab initio methods …”

Section: Introductionmentioning

confidence: 99%

UV Photochemistry of Thin Film and Matrix-Isolated Acetyl Chloride by Polarized FTIR

Rowland

Hess

1997

J. Phys. Chem. A

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A concerted HCl elimination reaction is observed following ultraviolet photoexcitation of neat and matrix-isolated samples of acetyl chloride. The photoreaction of condensed-phase acetyl chloride forms HCl·ketene complexes exclusively, in sharp contrast to the gas-phase photoreaction that produces Cl atoms, CH3CO, CH3, and CO. The reaction mechanism involves photoexcitation followed by S1 → S0 interconversion and a four-centered elimination on the ground electronic surface. The HCl·ketene complexes are the only primary photoproduct observed and are found to be aligned with the polarization axis of the irradiating laser. The polarization specific FTIR probe indicates that the HCl·ketene complexes form a T-shaped structure quite similar to the transition state structure recently calculated for HCl elimination from CH3COCl.

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“…The spin unrestricted second‐order Møller–Plesset perturbation theory (UMP2) 17–20 was adopted for the open shell system with 6‐311G** basis set. This choice of functional were made by the previous study 21, which shows that the effect of electron correlation on radical limit is quite appreciable and in fact a good estimate of the radical decomposition limits will be observed with the inclusion of electron correlation. Frequency calculations were performed to verify whether they are minima with all positive frequencies or TSs with imaginary frequency.…”

Section: Methodsmentioning

confidence: 99%

A theoretical study on decomposition and rearrangement reaction mechanism of trichloroacetyl chloride (CCl₃COCl)

Shankar

Kolandaivel

Senthilkumar

2010

Int J of Quantum Chemistry

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In the present study, the possible decomposition and rearrangement reaction profile of trichloroacetyl chloride have been studied using UMP2/6-311þþG (2d, 2p) level of ab initio and UB3LYP/6-311þþG (2d, 2p) level of density functional theory methods. The harmonic vibrational frequencies were calculated at the same level of theory used for the characterization of stationary points and zero-point vibrational energy corrections. The potential energy barrier and activation energy between each step of the reaction have been calculated for the seven possible reaction pathways (Ia-c, IIa-b, IIIa-b). The trichloroacetyl chloride is an asymmetric ketone where the two a bonds of acetyl chloride, the CAC and CACl bonds are strong with dissociation energy of 72 kcal/mol. The phosgene (COCl 2 ), dichloroketene (CCl 2 CO), carbon dichloride (CCl 2 ), carbon tetrachloride (CCl 4 ), and carbon monoxide (CO) are the major dominant products on the decomposition of the trichloroacetyl chloride. These resultant products are more hazards than the parent trichloroacetyl chloride molecules. The positive value of the reaction energy indicate that the overall reaction profile is found to be endothermic at the UMP2 and UBLYP/6-311þþG(2d, 2p) levels of theory, respectively, at UMP2/6-311G** optimized geometry.

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Dissociation dynamics of acetyl chloride and cis-trans isomerisation of methoxychloro carbene and chlorohydroxymetyl carbene

Cited by 19 publications

References 42 publications

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

UV Photochemistry of Thin Film and Matrix-Isolated Acetyl Chloride by Polarized FTIR

A theoretical study on decomposition and rearrangement reaction mechanism of trichloroacetyl chloride (CCl₃COCl)

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Dissociation dynamics of acetyl chloride and cis-trans isomerisation of methoxychloro carbene and chlorohydroxymetyl carbene

Cited by 19 publications

References 42 publications

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F–CH2Cl

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F–CH2Cl

UV Photochemistry of Thin Film and Matrix-Isolated Acetyl Chloride by Polarized FTIR

A theoretical study on decomposition and rearrangement reaction mechanism of trichloroacetyl chloride (CCl3COCl)

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Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH₂F–CH₂Cl

A theoretical study on decomposition and rearrangement reaction mechanism of trichloroacetyl chloride (CCl₃COCl)