Palladium-catalyzed carbon-carbon and carbon–heteroatom cross-coupling are some of the most widely applied reactions in contemporary organic synthesis, yet zero valent palladium coordinated by a single dative ligand proposed in myriad studies to be the most active form of these catalysts has not been unambiguously established. We report a viable synthetic route to palladium(0) complexes coordinated by a single monodentate ligand, tri(1-adamantyl)phosphine, through stoichiometric cationic or neutral boron-to-palladium transmetalation reactions that occur rapidly at cryogenic temperature. A combination of multinuclear NMR spectroscopic, X-ray crystallographic, EXAFS, and computation analyses support assignment of these species as 14-electron complexes coordinated either by the biaryl reaction product or a single solvent molecule. Synthetic access to these central intermediates provides new insights into catalyst speciation at the low valent stage of catalysis, which should be informative in studies of chemo- and site-selective oxidative addition reactions and ligand design to stabilize catalysts to strongly reducing, low coordinate transition metal intermediates.

Synthesis, characterization, and reactivity profiling of the monoligated active state of a palladium(0) catalyst

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.