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Author(s):   Zhou, Z.Y.; Fu, H.; Zhou, X.M.; Cheng, X.L.
Title:   Mechanistic investigation on the multi-channel reaction of Cl+CH2CO
Journal:   J. Mol. Struct. THEOCHEM
Volume:   620
Page(s):   207 - 214
Year:   2003
Reference type:   Journal article
Squib:   2003ZHO/FU207-214

Reaction:   H2C=C=O + ·ClHCl + HCCO
Reaction order:   2
Rate expression:   no rate data available
Category:  Theory
Data type:   Ab initio
Comments:   This reaction is abstraction like with a barrier of about 41 kcal/mol and being endothermic by about +6 kcal/mol.

No rate constants provided in this study. However, transition states with geometries, vibrational frequencies, energetics are computed - thus, rate expressions could be derived. Used DFT B3LYP/6-311++G(d,p) method. Looked at most possible channels for reaction of Cl with Ketene.

Barrierless addition channels with CH2Cl-C(O)* and ClC(O)-CH2* formation are exothermic by about 19 and 27 kcal/mol. Most favored overall reaction pathway is elimination of CO from the chemically activated CH2Cl-C(O)* (CH2Cl + CO products) being overall exothermic by about 8 kcal/mol and all intermediates and transition states being below the energy of the reactants. Next favored channel is 1,1 elimination of HCl from the hot CH2Cl-C(O)* (HCCO + HCl products) being slightly uphill endothermic by about 6 kcal/mol with all transition states lying at energies below the product energies.

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