We present a series of phosphine-ligated alkylpalladium(II) amido complexes that undergo thermal, concerted reductive elimination to form (sp3)C–N bonds. The effects of varying phosphine and amido ligands on the structure and reactivity of these complexes have been analyzed, and we have found examples of complexes that undergo reductive elimination with low free-energy barriers (&lt; 23 kcal/mol at 40 °C). Although multiple structures can exist in solution, reductive elimination occurs fastest from monometallic three-coordinate complexes, and the formation of these structures is most favored when ligated by tri-tert-butylphosphine. Reductive elimination also occurs directly from four-coordinate complexes bearing P-O bidentate ligands, although the free-energy barrier is significantly higher than that observed with the analogous complexes bearing tri-tert-butylphosphine. We believe that the results of this study will be of value to the design of catalysts for novel metal-catalyzed (sp3)C–N bond-forming reactions.

Phosphine-ligated alkylpalladium(II) amido complexes: Understanding the kinetic barrier to reductive elimination of alkylamines

253rd National Meeting (2017)

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