• Bulletin of the Korean Chemical Society
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• 제20권3호
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• pp.355-361
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• 1999

To improve the volatility and stability of lead complexes, the principle of stabilization by saturating the metal coordination sphere by intramolecular coordination through a β-diketonates with an ethereal group has was tested. Several new lead complexes with alkoxyalkyl-substituted β-diketonates, Pb(R1C(O)CHC(O)(CH2)3OR2)2(Rl=t-Bu, Me, OMe, i-Pr, R2=Me, Et), or carboxylate, Pb(OC(O)(CH2)3OEt)2, were prepared by the reaction between Pb(OAc)2 and corresponding alkoxyalkyl-substituted β-diketonates, and they were found to have a viscous liquid phase. The nature of the head (β-diketonate or carboxylate) or tails and substituents of β-diketonates appeared not to be important for the formation of the liquid phase. It is worth mentioning that Pb(OAc)2, which has limited use due to its low solubility, was successfully adopted as a starting material for the preparation of new lead complexes. Easy hydrolysis, reaction with HCl, and 13C NMR spectra indicated that tail portions were not coordinated to the metal as a copper derivative, Cu(t-BuC(O)CHC(O)(CH2)3OMe)2. All these complexes were not volatile enough for the MOCVD experiments, but a methyl derivative, Pb(MeC(O)CHC(O)(CH2)3OEt)2, showed some sublimation. The methoxy derivative, Pb(MeOC(O)CHC(O)(CH2)3OEt)2, was thermally unstable due to possible equilibrium between species coordinating with a keto oxygen atom and an ethereal atom of a methoxy group, which was confirmed by IR and 13C NMR spectra.

• Bulletin of the Korean Chemical Society
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• 제17권11호
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• pp.1023-1031
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• 1996

A new synthetic route for the lanthanum β-diketonate compounds via in-situ formed lanthanum alkyl complexes was developed in the process for the development of suitable MOCVD (metal-organic chemical vapor deposition) precursors of PLT, one of the promising material for the ferroelectric film. A series of lanthanum β-diketonate compounds were successfully synthesized by this method. This new method is found to have some merits; versatile method for almost every β-diketone, β-hydroxyketone, and β-hydroxyaldehyde, short reaction time, easy purification for high purity, moderate to high yield, and easy access to anhydrous compounds. In some cases, anhydrous oligomeric products fail to show the higher volatility. On the other hand, some lanthanum β-diketonates with aromatic groups such as La(1,3-biphenyl-l,3-propandione)3 are found to have favorable properties for a precursor of lanthanum oxide, one of major components of PLT, such as low melting point, and much higher decomposition temperature. A plausible pyrolysis mechanism is proposed by the TGA, where consecutive dissociation of R, CO, CH, C, and O fragments occurs.

• Bulletin of the Korean Chemical Society
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• 제24권5호
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• pp.535-536
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• 2003

• The Korean Journal of Ceramics
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• 제6권4호
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• pp.370-379
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• 2000

Simple ways to build up mixed-metal molecules which can act as potential single-source precursors to multimetallic oxides are reviewed. Emphasis is given to Lewis acid-base reactions between metal alkoxides M(OR)/sub n/, and between metal alkoxides and more accessible oxide precursors, carboxylates M(O₂CR)/sub n/ and β-diketonates M(β-dik)/sub n/. Characterization of the precursors is achieved in the solid state (single crystal X-ray diffraction, FT-IR) and by multinuclear NMR in solution. The reactions proceed toward the formation of aggregates in which the different metals display their usual coordinations numbers, often six for transition metals, as shown. Strategies for fixing the stoichiometry between the metals are developed. The reactivity of the MM species (dissociation, effects of chemical modifiers, of other metallic species, hydrolytic or non-hydrolytic condensation, etc.) will be indicated. Transformations into oxides are illustrated on precursors for titanates or niobates.