Palladium Bisphosphine Monoxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance

• DOI: 10.1021/jacs.4c10718
• Publication Date: 2024-12-17T08:13:45Z
• Authors: Shenghua Yang; Min Deng; Ryan A. Daley; Andrea Darù; William J. Wolf; David T. George; Senjie Ma; Bryn K. Werley; Erika Samolova; Jake B. Bailey; Milan Gembicky; Jonathan Marshall; Steven R. Wisniewski; Donna G. Blackmond; Keary M. Engle
• Keywords: Scope (computer science); Relevance

Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation formation of the catalytically active species, with potentially widespread relevance number catalytic systems. We examine internal redox reaction PdII(bisphosphine)X2 (X = Cl, OAc, etc.) complexes to reveal previously underexplored aspects bisphosphine monoxides (BPMOs), including evaluation structure and development general conditions access collection structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, series PdII(BPMO)(R)(X) (R aryl, alkyl; X I, Br) bearing 24 different ligands were characterized by NMR X-ray crystallography. Comparison performance versus as is demonstrated be an enabling diagnostic tool Pd development. Finally, differences behavior between monoxide rationalized through solid-state parametrization stoichiometric experiments.