Reaction of (POR) M(OAc)2 (M = Zr, Hf) with nBuLi and solid state structure of [(TPP)Zr(μ-OH)2]2

Article abstract of DOI:10.1016/0022-328X(95)05835-D

A general route to (TPP)Zr(OAc)₂, (OEP)Zr(OAc)₂ and (TPP)Hf(OAc)₂ from the reaction of MCl₄ and H₂(POR) in benzonitrile, followed by treatment with pyridine + acetic acid is described. The reaction of (POR)M(OAc)₂ with ⁿBuLi occurs in a stepwise manner, with approximately 2 equiv. of ⁿBuLi required before the formation of M(ⁿBu) is observed, and 4 equiv. required for stoichiometric conversion to (POR)M(ⁿBu)₂. The tetrahydroxo-bridged dimer [(TPP)Zr(μ-OH)₂]₂ was obtained as the benzene solvate from the hydrolysis of (TPP)Zr(ⁿBu)₂, and the structure was determined by single crystal X-ray diffraction (triclinic, P1; a = 10.606(2) A, b = 13.003(3) A, c = 14.587(3) A, α = 99.85(3)°, β = 107.61(3)°, γ = 96.82(3)°, Z = 2).