The reactions of the heteroleptic zirconium diisopropoxide bis(acetylacetonate) in benzene solution with two equivalents of oximes, alkoxyalkanols, triphenylsilanol and trimethylsilyl acetate yield products with the formula [{MeC(O)CHC(O)Me}2ZrL2] with L = -ONC(Me)C5H4N-2, -ONC(Me)C4H3O-2, -OCH2CH2OR (R = Me, Et, Bun; py = pyridine, fu = furan), -OSiPh3 and -OSiMe3. Most of these derivatives are solids, but the [(acac)2Zr(OSiMe3)2] is a viscous oil. They could be purified either by recrystallization or by vacuum distillation; all of these are monomeric in boiling benzene. Their elemental analyses, molecular weight measurements and IR as well as NMR spectra were measured. The oximato complex [(acac)2Zr{ONC(Me)py-2}2] has been shown by single crystal X-ray crystallography to be monoclinic and mononuclear in the solid state, where zirconium has the coordination number 8; all the ligands are situated in cis- position and the oximato ligand binds via N and O in a dihapto (η2-N,O) manner.