We present the concerted reductive elimination of alkylamines from a series of <i>syn-</i>2-methylnorbornylpalladium(II) and neopentylpalladium(II) amido complexes bearing phosphine ancillary ligands. Variations of the ligand structures in these complexes has enabled an analysis of the steric and electronic factors which control the speciation of the metal complex and the kinetic barrier to reductive elimination. The rate of reductive elimination from complexes bearing unhindered and electron-rich anilido ligands is faster than that from complexes bearing hindered or electron-deficient anilido ligands. Three-coordinate complexes react faster than four-coordinate complexes, but the reaction can still proceed in good yield when the second ancillary is a weak donor such as an ether. The flexibility of these bidentate ligands was found to be a key factor controlling the barrier to reductive elimination. Ongoing studies seek to apply these results to complexes more relevant to catalytic reactions.

Reductive elimination of alkylamines from phosphine-ligated alkylpalladium(II) amido complexes

254th National Meeting (2017)

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