Document Detail

"Inverse-electron-demand" ligand substitution: experimental and computational insights into olefin exchange at palladium(0).
MedLine Citation:
PMID:  15535709     Owner:  NLM     Status:  MEDLINE    
The mechanism of olefin substitution at palladium(0) has been studied, and the results provide unique insights into the fundamental reactivity of electron-rich late transition metals. A systematic series of bathocuproine-palladium(0) complexes bearing trans-beta-nitrostyrene ligands (ns(X) = X-C(6)H(4)CH=CHNO(2); X = OCH(3), CH(3), H, Br, CF(3)), (bc)Pd(0)ns(X) (3(X)), was prepared and characterized, and olefin-substitution reactions of these complexes were found to proceed by an associative mechanism. In cross-reactions between (bc)Pd(ns(CH)()3) and ns(X) (X = OCH(3), H, Br, CF(3)), more-electron-deficient olefins react more rapidly (relative rate: ns(CF)()3 > ns(Br) > ns(H) > ns(OCH)()3). Density functional theory calculations of model alkene-substitution reactions at a diimine-palladium(0) center reveal that the palladium center reacts as a nucleophile via attack of a metal-based lone pair on the empty pi orbital of the incoming olefin. This orbital picture contrasts that of traditional ligand-substitution reactions, in which the incoming ligand donates electron density into an acceptor orbital on the metal. On the basis of these results, olefin substitution at palladium(0) is classified as an "inverse-electron-demand" ligand-substitution reaction.
Brian V Popp; Joseph L Thorman; Christine M Morales; Clark R Landis; Shannon S Stahl
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  126     ISSN:  0002-7863     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2004 Nov 
Date Detail:
Created Date:  2004-11-10     Completed Date:  2004-12-28     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  14832-42     Citation Subset:  IM    
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
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MeSH Terms
Alkenes / chemistry*
Alkynes / chemistry
Benzene Derivatives / chemistry
Magnetic Resonance Spectroscopy
Models, Chemical
Models, Molecular
Organometallic Compounds / chemistry*
Palladium / chemistry*
Phenanthrolines / chemistry
Styrenes / chemistry
Grant Support
1S10 RR 04981-01/RR/NCRR NIH HHS; 1S10 RR 08389-01/RR/NCRR NIH HHS
Reg. No./Substance:
0/Alkenes; 0/Alkynes; 0/Benzene Derivatives; 0/Ligands; 0/Organometallic Compounds; 0/Phenanthrolines; 0/Styrenes; 102-96-5/beta-nitrostyrene; 4733-39-5/bathocuproine; 7440-05-3/Palladium

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