920508-91-4Relevant articles and documents
Relative rates for the amination of η3-allyl and η3-benzyl complexes of palladium
Johns, Adam M.,Tye, Jesse W.,Hartwig, John F.
, p. 16010 - 16011 (2007/10/03)
Reactions of nucleophiles with metal-bound hydrocarbyl π-ligands bound in an η3-fashion are key steps in a variety of carbon-carbon and carbon-heteroatom bond-forming reactions. To reveal factors that control the rates of reaction of nucleophiles with this type of ligand, the rates of reactions of an aromatic and an aliphatic amine with a series of η3-allyl, η3-benzyl, and η3-phenethyl palladium complexes ligated by the bisphosphine (R)-BINAP to form allylic and benzylic amines were measured. These data showed that the less common addition to an η3-benzyl complex is faster than the more common addition to an η3-allyl complex. The relative rates of reaction followed the trend naphthylmethyl > naphthylethyl > benzyl > 1,1-dimethylallyl > allyl. Computational studies suggest that there is a correlation between the amount of positive charge at the site of nucleophilic attack and the rate of C-N bond formation. Copyright
