4.8 Article

Diagonally Related s- and p-Block Metals Join Forces: Synthesis and Characterization of Complexes with Covalent Beryllium-Aluminum Bonds

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 33, Pages 11459-11463

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201906609

Keywords

aluminum; beryllium; DFT calculations; low oxidation state; metal-metal bonding

Funding

  1. Australian Research Council
  2. U.S. Air Force Asian Office of Aerospace Research and Development [FA2386-18-1-0125]
  3. Alexander von Humboldt Foundation

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Additions of beryllium-halide bonds in the simple beryllium dihalide adducts, [BeX2(tmeda)] (X=Br or I, tmeda=N,N,N ',N '-tetramethylethylenediamine), across the metal center of a neutral aluminum(I) heterocycle, [:Al((Dip)Nacnac)] ((Dip)Nacnac=[(DipNCMe)(2)CH](-), Dip=2,6-diisopropylphenyl), have yielded the first examples of compounds with beryllium-aluminum bonds, [((Dip)Nacnac)(X)Al-Be(X)(tmeda)]. For sake of comparison, isostructural Mg-Al and Zn-Al analogues of these complexes, viz. [((Dip)Nacnac)(X)Al-M(X)(tmeda)] (M=Mg or Zn, X=I or Br) have been prepared and structurally characterized. DFT calculations reveal all compounds to have high s-character metal-metal bonds, the polarity of which is consistent with the electronegativities of the metals involved. Preliminary reactivity studies of [((Dip)Nacnac)(Br)Al-Be(Br)(tmeda)] are reported.

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