Mononuclear gallium complexes with the redox-active dmp-bian ligand (dmp-bian is 1,2-bis[(2,6-dimethylphenyl)imino]acenaphthene): synthesis and reactions with alkynes

Abstract

The direct reduction of 1,2-bis[(2,6-dimethylphenyl)imino]acenaphthene (dmp-bian (1)) with gallium metal in toluene affords the solvent-free bis-ligand complex [(dmp-bian)2Ga] (2), in which two diimine ligands are in different oxidation states (radical-anionic and dianionic). The addition of phenylacethylene to the Ga–N–C moiety of the dianionic ligand of compound 2 gives the complex [(dmp-bian)Ga(HC=CPh)(dmp-bian)] (3), in which new Ga–C and C–C bonds are formed. The reaction of 2 with hex-1-yne produces the gallium dialkynyl complex [(dmp-bian)Ga(C≡C–Bu)2] (4), with the metal atom bonded to the dmp-bian radical anion. Paramagnetic compounds 24 were characterized by ESR spectroscopy and X-ray diffraction. The known compound dmp-bian was structurally characterized for the first time.

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Correspondence to A. A. Skatova.

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Dedicated to Academician of the Russian Academy of Sciences A. I. Konovalov on the occasion of his 85th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0275–0283, February, 2019.

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Skatova, A.A., Bazyakina, N.L., Fedushkin, I.L. et al. Mononuclear gallium complexes with the redox-active dmp-bian ligand (dmp-bian is 1,2-bis[(2,6-dimethylphenyl)imino]acenaphthene): synthesis and reactions with alkynes. Russ Chem Bull 68, 275–283 (2019). https://doi.org/10.1007/s11172-019-2383-9

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Key words

  • gallium
  • acenaphthene-1,2-diimines
  • redox-active ligands
  • synthesis
  • structure
  • X-ray diffraction