Mechanistic diversity in thermal fragmentation reactions: a computational exploration of CO and CO2 extrusions from five-membered rings

Rzepa, Henry S. and Wentrup, Curt (2013) Mechanistic diversity in thermal fragmentation reactions: a computational exploration of CO and CO2 extrusions from five-membered rings. Journal of Organic Chemistry, 78 15: 7565-7574. doi:10.1021/jo401146k


Author Rzepa, Henry S.
Wentrup, Curt
Title Mechanistic diversity in thermal fragmentation reactions: a computational exploration of CO and CO2 extrusions from five-membered rings
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2013-08-01
Sub-type Article (original research)
DOI 10.1021/jo401146k
Volume 78
Issue 15
Start page 7565
End page 7574
Total pages 10
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Formatted abstract
The mechanisms of a variety of thermal pericyclic fragmentation reactions of five-membered heterocyclic rings are subjected to scrutiny at a density functional level by computation of transition state free energy barriers and intrinsic reaction coordinates (IRCs). The preferred computed products generally match those observed in flash vacuum thermolysis experiments. For certain reactions, which also have the highest reaction temperatures and computed barriers, a degree of multireference character to the wave function manifests in an overestimation of the DFT-computed barrier, with a more reasonable barrier obtained by a CASSCF single point energy calculation. Many of the IRCs exhibit "hidden intermediates" along the reaction pathway, but conversely reactions that could be considered to involve the formation of an intermediate nitrene prior to alkyl or aryl migration show no evidence of such an intermediate. Such exploration of the diversity of behavior in a class of compounds using computational methods with interactive presentation of the results within the body of a journal article is suggested as being almost a sine qua non for laboratory-based research on reactive intermediates. 
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
 
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