LIGAND-EXCHANGE REACTIONS OF DIMETHOXOBIS (ACETYLACETONATO)ZIRCONIUM WITH ALKYL ACETOACETATE AND TRICARBONYL COMPOUNDS

Title reactions have been conducted in benzene. Ethyl acetoacetate rea cted with the Zr-OMe group of dimethoxobis(acetylacetonato) zirconium, Zr(OMe)(2)(acac)(2), to afford the disproportionation products bearin g a Zr-OMe group. However, the reaction with methyl acetoacetate (Hmta c) led to the formation of the Zr(mtac)(2)(acac)(2) containing a small amount of Zr-OMe group. The reactions of Zr(OMe)(2)(acac)(2) with tri carbonyl compounds (HL) such as 3-acetyl-2,4-pentanedione (Hacacac) an d 3-ethoxycarbonyl-2,4-pentanedione (Hecacac) in a 1:2 molar ratio pro ceeded smoothly to afford the corresponding Zr(L)(2)(acac)(2) in high yield. The Zr(L)(2)(acac)(2) complex was not obtained from the reactio n between Zr(acac)(4) and HL in the molar ratio. The Zr(L)(4) complex was produced in high yield from the reaction of Zr(OMe)(2)(acac)(2) or Zr(acac)(4) with an excess amount of HL. The solubility of the isolat ed Zr-complexes for aprotic solvent was examined.