Ligand design represents a central tenet of synthetic chemistry, wherein simple modification can lead to major differences in reactivity. Recently, our group reported a new diphosphine ligand, P2BCy4 (1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane), which contains four pendant boranes. By surrounding a metal center with the P2BCy4 ligand, we have influenced reactivity at the primary coordination sphere. From a saturated 18-electron complex, [Ni0(P2BCy4)2], we provide examples of elementary reactions: oxidative addition and protonation that showcase how divergent - and unique - reactivity can be achieved using the P2BCy4 scaffold. Approaches using other metals (non-nickel) will also be highlighted as well as preliminary results from density functional theory (DFT) studies that explore the ligand's role in such transformations.

Surrounding nickel with a Lewis acidic secondary coordination sphere

ACS Fall 2021

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