Document Detail


Correlation of relative rates of PdCl(2) oxidation of functionalized acyclic alkenes versus alkene ionization potentials, HOMOs, and LUMOs.
MedLine Citation:
PMID:  11456754     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Investigations of the title reaction, carried out by plotting logs of the relative reaction rates vs IPs, vs HOMOs, and vs LUMOs, reveal multiple nearly parallel lines of correlation with small negative slopes in each. Overall, the natural grouping into monosubstituted and disubstituted alkenes gives better correlations than that obtained by using all alkenes. Comparison with analogous plots for other reactions indicates that the mechanism for this reaction has similarities to that for hydroboration, the major difference being that the lines in the plots for hydroboration have positive slopes, indicating an electrophilic rate-determining step involving the pi electrons, while those for the title reaction have small negative slopes, indicating a nucleophilic rate-determining step. Of the two reaction mechanisms proposed for the title reaction, only one has a nucleophilic attack at the complexed alkene as the rate-determining step, and therefore, this work supports that reaction mechanism.
Authors:
D J Nelson; R Li; C Brammer
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  123     ISSN:  0002-7863     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2001 Feb 
Date Detail:
Created Date:  2001-07-17     Completed Date:  2001-10-11     Revised Date:  2003-10-31    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1564-8     Citation Subset:  -    
Affiliation:
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
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