A Next-Generation Air-Stable Palladium(I) Dimer Enables Olefin Migration and Selective C-C Coupling in Air

We report a new air-stable Pd^I dimer, [Pd(μ-I)(PCy₂ ^t Bu)]₂ , which triggers E-selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C-C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C-Br, C-OTf/OFs, and C-Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous Pd^I dimer generations for substrates that bear substituents ortho to C-OTf.