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

A general route to (TPP)Zr(OAc)(2), (OEP)Zr(OAc)(2) and (TPP)Hf(OAc)(2) from the reaction of MCl(4) and H-2(POR) in benzonitrile, followed by treatment with pyridine + acetic acid is described. The reaction of(POR)M(OAc)(2) with (n)BuLi occurs in a stepwise manner, with approximately 2 equiv. of (n)BuLi required before the formation of M((n)Bu) is observed, and 4 equiv. required for stoichiometric conversion to (POR)M((n)Bu)(2). The tetrahydroxo-bridged dimer [(TPP)Zr(mu-OH)(2)](2) was obtained as the benzene solvate from the hydrolysis of (TPP)Zr((n)Bu)(2), and the structure was determined by single crystal X-ray diffraction (triclinic, <P(1)over bar>; a=10.606(2) Angstrom,b=13.003(3) Angstrom, c=14.587(3) Angstrom, alpha=99.85(3)degrees, beta=107.61(3)degrees, gamma=96.82(3)degrees, Z=2).