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Photoactivated α‐ketocarbenes: Formation and isomerization reactions. RRKM calculations with semi‐empirical parameters (AM1, MNDOC)
Author(s) -
Bachmann Christian,
N'Guessan Thomas Yao
Publication year - 1994
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550260606
Subject(s) - chemistry , isomerization , ketene , quantum , photodissociation , ketone , relaxation (psychology) , rrkm theory , computational chemistry , wolff rearrangement , reaction rate constant , photochemistry , kinetics , quantum mechanics , medicinal chemistry , organic chemistry , physics , psychology , social psychology , catalysis
The dynamical aspects of some α‐diazoketones (DZ) photolysis are investigated within the framework of statistical theories (RRKM formulation). On the whole, the results agree satisfactorily with the gas‐phase experimental observations (quantum yields). In particular, the reactions DZ + hv → α‐ketocarbene (KC) + N 2 , appear to be mainly governed by statistical behavior. The two channel isomerizations KC → ketene (KE), i.e, the Wolff Rearrangement, and KC → α,β‐unsaturated ketone (ON) are also considered. It is suggested that the trapping of the α‐ketocarbenes and oxirenes (OX) species would be favored under appropriate conditions (among them the irradiation wavelength and the relaxation processes involved in the reactive medium). The parametrization of the model relies on semi‐empirical quantum calculations and is improved by some adjustments with experimental data. © 1994 John Wiley & Sons, Inc.