title: Intermolecular insertion of ethylene and octene into a palladium-amide bond. Spectroscopic evidence for an ethylene amido intermediate.
abstract: We report a series of palladium diarylamido complexes containing a cyclometalated phosphine ligand and a coordinated THF that form enamine products from migratory insertion of ethylene and octene into the metal-nitrogen bond. The reactions of these complexes were sensitive to the electronic properties of the diarylamido group. The complex with the more electron-donating amido ligand reacted nearly 2 orders of magnitude faster than the complex with the least electron-donating amido group. The mechanism of the reactions with alkenes involves exchange of olefin for THF, as revealed by the positive order of the reaction in alkene and inverse order in the concentration of THF. A syn-aminopalladation that would result from migratory insertion was revealed by the stereochemistry of the enamine product resulting from reaction with cis-ethylene-d(2). Finally, a three-coordinate THF-free species was isolated from a synthesis of the amido complex in aromatic solvents, and spectroscopic evidence for an ethylene amido species was gained, in part by the addition of H(2)(13)C=(13)CH(2) to the three-coordinate amido complex at -100 degrees C.
authors.affiliation: Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
authors.forename: Patrick S
authors.initials: PS
authors.lastname: Hanley
authors.forename: Dean
authors.initials: D
authors.lastname: Marković
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig