Poly(pyrazolyl)aluminate complexes containing aluminum-hydrogen bonds |
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Authors: | Snyder Christopher J Heeg Mary Jane Winter Charles H |
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Institution: | Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States. |
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Abstract: | The treatment of LiAlH(4) with 2, 3, or 4 equiv of the 3,5-disubstituted pyrazoles Ph(2)pzH or iPr(2)pzH afforded Li(THF)(2)]AlH(2)(Ph(2)pz)(2)] (97%), Li(THF)]AlH(Ph(2)pz)(3)] (96%), Li(THF)(4)]Al(Ph(2)pz)(4)] (95%), and Li(THF)]AlH(iPr(2)pz)(3)] (89%). The treatment of ZnCl(2) with Li(THF)]AlH(Ph(2)pz)(3)] afforded Zn(AlH(Ph(2)Pz)(3))H (70%). X-ray crystal structures of these complexes demonstrated κ(2) or κ(3) coordination of the aluminum-based ligands to the Li or Zn ions. The treatment of Li(THF)]AlH(Ph(2)pz)(3)] with MgBr(2) or CoCl(2) in THF/Et(2)O solutions, by contrast, afforded the pyrazolate transfer products Mg(2)Br(2)(Ph(2)pz)(2)(THF)(3)·2THF (25%) and Co(2)Cl(2)(Ph(2)pz)(2)(THF)(3)·THF (23%) as colorless and blue crystalline solids, respectively. An analogous treatment of Li(THF)]AlH(Ph(2)pz)(3)] with MCl(2) (M = Mn, Fe, Ni, Cu) afforded metal powders and H(2), illustrating hydride transfer from Al to M as a competing reaction path. |
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