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Home ©NIST, 2013 Accessibility information |
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 + Cl → ClCH(.)CHO
Reaction order:
2
Rate expression:
no rate data available
Category: Theory
Data type:
Ab initio
Comments:
This is a sequential step reaction with a barrieless of addtion of Cl followed by migration of Cl with the reaction being overall exothermic by about 19 kcal/mol, but with a significant barriers of about 23 kcal/mol relative to the reactants (and 42 kcal/mol relative to the CH2ClC(O) intermediate).
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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