We report here the remarkable properties of PAd(3), a crystalline air-stable solid accessible through a scalable S(N)1 reaction. Spectroscopic data reveal that PAd(3), benefiting from the polarizability inherent to large hydrocarbyl groups, exhibits unexpected electron releasing character that exceeds other alkylphosphines and falls within a range dominated by N-heterocyclic carbenes. Dramatic effects in catalysis are also enabled by PAd(3) during Suzuki Miyaura cross-coupling of chloro(hetero)arenes (40 examples) at low Pd loading, including the late stage functionalization of commercial drugs. Exceptional space-time yields are demonstrated for the syntheses of industrial precursors to valsartan and boscalid from chloroarenes with similar to 2 x 10(4) turnovers in 10 min.