%0 Generic %A Hanley, Patrick S. %A Hartwig, John F. %D 2011 %T Intermolecular Migratory Insertion of Unactivated Olefins into Palladium–Nitrogen Bonds. Steric and Electronic Effects on the Rate of Migratory Insertion %U https://acs.figshare.com/articles/dataset/Intermolecular_Migratory_Insertion_of_Unactivated_Olefins_into_Palladium_Nitrogen_Bonds_Steric_and_Electronic_Effects_on_the_Rate_of_Migratory_Insertion/2607529 %R 10.1021/ja205722f.s001 %2 https://acs.figshare.com/ndownloader/files/4257046 %K alkene %K ethylene vs THF %K Intermolecular Migratory Insertion %K cyclometalated benzylphosphine ligands %K palladium amido complexes %K Migratory InsertionWe report %K insertion step %K binding %K rate constants cause %K vinylarene %K steric properties %X We report a detailed examination of the effect of the steric and electronic properties of the ancillary ligand and the alkene reactant on the rate of migratory insertion of unactivated alkenes into the palladium–nitrogen bond of isolated palladium amido complexes. A series of THF-bound and THF-free amidopalladium complexes ligated by cyclometalated benzylphosphine ligands possessing varied steric and electronic properties were synthesized. The THF-free complexes react with ethylene at −50 °C to form olefin-amido complexes that were observed directly and that undergo migratory insertion, followed by β-hydride elimination to generate enamine products. The effect of the steric properties of the ancillary ligand on the binding of the alkene and the rate of migratory insertion were evaluated individually. The relative binding affinity of ethylene vs THF is larger for the less sterically hindered complex than for the more hindered complex, but the less hindered complex undergoes the insertion of ethylene more slowly than does the more hindered complex. These two changes in relative equilibrium and rate constants cause the rates of reaction of ethylene with the two THF-ligated species having different steric properties to be similar to each other. Reactions of the complexes containing electronically varied ancillary ligands showed that the more electron-poor complexes underwent the migratory insertion step faster than the more electron-rich complexes. Reactions of a THF-ligated palladium-amide with substituted vinylarenes showed that electron-poor vinylarenes reacted with the amido complex slightly faster than electron-rich vinylarenes. Separation of the energetics of binding and insertion indicate that the complex of an electron-rich vinylarene is more stable in this system than the complex of a more electron-poor vinylarene but that the insertion step of the bound, electron-rich vinylarene is slower than the insertion step with the bound, electron-poor vinylarene. %I ACS Publications