Synthesis and Reaction Chemistry of Zinc‐Diarylphosphido Clusters with Phosphorus Precursors

The synthesis of the zinc phosphido clusters [Zn 2 (µ‐PPh 2 ) 2 (PPh 2 ) 2 (NC 5 H 5 ) 2 ] (1) and [Zn 4 (µ‐PPh 2 ) 4 (OAc) 4 (NC 5 H 5 ) 2 ] (2) is presented. The clusters are accessed via the reaction of Zn(OAc) 2 with differing amounts of Me 3 SiPPh 2 . When 1 was heated under solvothermal conditions in pyridine, it yielded micrometer sized metallic zinc crystals via the reduction of Zn II by the diphenylphosphido ligands, forming tetraphenyldiphosphine as a by‐product. When white phosphorus (P 4 ) was added to this reaction, soluble, micrometer‐sized aggregates of zinc phosphides were produced. Reacting 2 with P(SiMe 3 ) 3 at room temperature yields a mixture of phosphido and phosphinidene species. Under solvothermal conditions with P(SiMe 3 ) 3 , tetraphenyldiphosphine was again observed together with aggregates of zinc phosphides.