Linked Life Data

12889962

Source:http://linkedlifedata.com/resource/pubmed/id/12889962

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
31
pubmed:dateCreated
2003-7-31
pubmed:abstractText
The effects of aromatic stabilization on the rates of [1,5]-hydrogen shifts in a series of carbo- and heterocyclic dihydroaromatic compounds were estimated by B3LYP/6-31G computations. The aromatic stabilization energy of the product is directly translated into increased exothermicity of these reactions. Relative trends for a significant range of endothermic and exothermic [1,5]-shifts with different intrinsic activation energies are reliably described by Marcus theory. The effects of aromaticity or antiaromaticity are very large and can lead to dramatic acceleration or deceleration of [1,5]-hydrogen shifts and even to complete disappearance of the reaction barrier. Not only the activation energy but the shape and position of the reaction barrier can be efficiently controlled by changes in the aromaticity of the products, making these systems interesting models for studying hydrogen tunneling. Marcus theory can also be applied successfully to other pericyclic shifts such as [1,5]-shifts which involve chlorine and methyl transfer.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Aug
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
6
pubmed:volume
125
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
9329-42
pubmed:year
2003
pubmed:articleTitle
Control of kinetics and thermodynamics of [1,5]-shifts by aromaticity: a view through the prism of Marcus theory.
pubmed:affiliation
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. alabugin@chem.fsu.edu
pubmed:publicationType
Journal Article