Linked Life Data

20831167

Source:http://linkedlifedata.com/resource/pubmed/id/20831167

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
39
pubmed:dateCreated
2010-9-30
pubmed:abstractText
Non-TST behavior has recently attracted a great deal of attention. If such behavior is general, then the standard way in which synthetic chemists rationalize and predict reactivity and selectivity would be at least partially invalid. The work in this article was inspired by recent results which highlighted a departure from the predictions of TST for rationalization of the regiochemical outcome of the hydroboration reaction mechanism, suggesting that the isomeric product ratios arise because of nonstatistical dynamical effects (J. Am. Chem. Soc. 2009, 131, 3130-3131). We suggest, based on new calculations using a weak collision RRKM-Master Equation (ME) model, an alternative interpretation of the experimental results which preserves a statistical reaction model. While it is a common assumption that all intermediates and transition states along the reaction path are in thermal equilibrium with solvent, our ME results show that hot intermediates may react while they are undergoing stepwise relaxation through weak collisions, even in solution. To our knowledge, this work represents the first application of master equation methodology to a solution phase thermal reaction in organic chemistry that cannot be otherwise explained using conventional TST. Explicit modeling of solvent and solute dynamics is often prohibitively expensive; however, the master equation offers a computationally tractable model with considerable predictive power that may be utilized to investigate whether stepwise collisional relaxation is prevalent in other polyatomic systems.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Oct
pubmed:issn
1520-5126
pubmed:author
pubmed:issnType
Electronic
pubmed:day
6
pubmed:volume
132
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
13621-3
pubmed:meshHeading
pubmed:year
2010
pubmed:articleTitle
Alkene hydroboration: hot intermediates that react while they are cooling.
pubmed:affiliation
School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom. david.r.glowacki@bristol.ac.uk
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't