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Poly(pyrazolyl)aluminate complexes containing aluminum-hydrogen bonds.

Christopher J Snyder1, Mary Jane Heeg, Charles H Winter

  • 1Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.

Inorganic Chemistry
|September 1, 2011
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Lithium aluminum hydride reacts with pyrazoles to form novel aluminum complexes. These complexes undergo pyrazolate transfer or hydride transfer reactions with various metal salts, yielding diverse metal-organic compounds.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Inorganic Synthesis

Background:

  • Lithium aluminum hydride (LiAlH4) is a versatile reducing agent.
  • Pyrazoles are versatile ligands in coordination chemistry.
  • The reactivity of LiAlH4 with substituted pyrazoles is not fully explored.

Purpose of the Study:

  • To synthesize and characterize novel aluminum complexes using LiAlH4 and substituted pyrazoles.
  • To investigate the reactivity of these aluminum complexes with various metal halides.
  • To explore pyrazolate and hydride transfer reactions.

Main Methods:

  • Reaction of LiAlH4 with 3,5-disubstituted pyrazoles (Ph2pzH, iPr2pzH) in THF.
  • Treatment of synthesized aluminum complexes with metal chlorides (ZnCl2, MgBr2, CoCl2, MnCl2, FeCl2, NiCl2, CuCl2).
  • Characterization of products using X-ray crystallography.

Main Results:

  • Formation of novel lithium aluminum complexes with varying pyrazolate ligands.
  • Synthesis of a zinc complex, Zn(AlH(Ph2Pz)3)H, via pyrazolate transfer.
  • Observation of pyrazolate transfer to Mg and Co, and competing hydride transfer to Mn, Fe, Ni, and Cu, producing metal powders and H2.

Conclusions:

  • The reaction of LiAlH4 with pyrazoles provides access to a range of aluminum complexes.
  • These complexes exhibit diverse reactivity, undergoing either pyrazolate or hydride transfer depending on the metal halide.
  • The study highlights the utility of pyrazolate ligands in forming novel organometallic structures.