Characterization and interconversion of metal-phosphorus single and double bonds: Bis(cyclopentadienyl)zirconium and -hafnium bis(diorganophosphide) complexes

Article abstract of DOI:10.1021/om50002a022

Two equivalents of LiPR₂ react with (η-C⁵H₅)₂MCl₂, affording (η-C₅H₅)₂M(PR₂)₂ (M = Zr, Hf; R = ethyl, cyclohexyl (Cy), or phenyl). ³¹P NMR and X-ray structural results indicate that these complexes contain both single and double metal-phosphorus bonds which interconvert in solution. Sodium naphthalenide reduction of these complexes produces the corresponding Zr^III and Hf^III complexes [(η-C₅H₅)₂M(PR₂)₂] [Na(THF)_n]; a bis(μ-diorganophosphido) heterobimetallic structure is proposed.