Gallium Complexes with Acenaphthene-1-Imino-2-one: Synthesis and Reactivity

Abstract

The reduction of acenaphthene-1-(2,6-diisopropylphenyl)imino-2-one (Dpp-Mian) by gallium in the presence of iodine primarily results in a bis(ligand) paramagnetic derivative [(Dpp-Mian)₂GaI] and then to a dimeric diamagnetic complex [(Dpp-Mian)GaI]₂, the reaction of which with PhC≡CH gives a cycloaddition product [{Dpp-Mian(HC=CPh)}GaI]₂. The new compounds are characterized by IR spectroscopy and ¹H NMR spectroscopy. The structures of complexes (Dpp-Mian)₂GaI and [{Dpp- Mian(HC=CPh)}GaI]₂ are determined by X-ray structure analysis (CIF files CCDC nos. 1571860 and 1571861, respectively). The catalytic activity tests for compounds [(Dpp-Mian)GaI]₂ and [{Dpp-Mian(HC=CPh)}GaI]₂ are conducted in the reactions of 4-chloroaniline with phenylacetylene and carbodiimide and in the reaction of phenylacetylene with 1-naphthol.