Zirconium-Catalyzed Heterodehydrocoupling of Primary Phosphines with Silanes and Germanes

Triamidoamine-supported zirconium complexes catalyze the heterodehydrocoupling of primary phosphines with silane and germanes. In this catalysis, P−Si or P−Ge products are observed exclusively with no competitive P−P bond formation. Phosphido complexes (N3N)ZrPHR (N3N = N(CH2CH2NSiMe3)33-, R = Ph, 2; Cy, 3) were observed to be the catalyst resting state, and complex 2 was structurally characterized.