Tris(bicyclo[1.1.1]pentyl)phosphine: An Exceptionally Small Tri-tert-alkylphosphine and Its Bis-Ligated Pd(0) Complex

Tris(bicyclo[1.1.1]pentyl)phosphine can be prepared by radical addition of PH₃ to [1.1.1]propellane, giving the smallest tri-tert-alkylphosphine known. PBcp₃ is substantially smaller than PCy₃ and is comparable in electron-donating power to PEt₃. It gives a bis-ligated Pd(0) complex Pd(PBcp₃)₂ that is exceptionally reactive toward alkyl halide oxidative addition and functions as a general ligand for palladium-catalyzed cross-coupling of sp³ electrophiles. Radical addition of [1.1.1]propellane to phenylphosphine gives the bis(bicyclo[1.1.1]pentyl)phosphine derivative PBcp₂Ph, illustrating the generality of this approach to bicyclopentylphosphine synthesis.