The reactivity of gallium(i) and indium(i) halides towards bipyridines, terpyridines, imino-substituted pyridines and bis(imino)acenaphthenes

Abstract

“GaI” reacts with 2,2′-bipyridine (bipy) to give salts of composition [Ga(bipy)₃][I]₃, [{(bipy)₂Ga}₂(μ-OH)₂]₂[Ga₂I₆][I]₆ or [{(bipy)₂Ga}₂(μ-OH)₂][I]₄, depending upon the reaction conditions. “GaI” also reacts with 4′-phenyl-2,2′∶6′,2″-terpyridine (Phterpy) to give the salt [GaI₂(Phterpy)][I]. When “GaI” is treated with the imino-substituted pyridines RNC(H)Py, Py = 2-pyridyl, R = Ar (C₆H₃Prⁱ₂-2,6) or Bu^t, a reductive coupling of the CN functionality occurs to give the diamido-digallium(III) complexes [{I₂Ga[η²-(Py)(NR)C(H)]}₂]. In contrast, InCl reacts with ArNC(H)Py to give an adduct, [InCl₃(THF){η²-ArNC(H)Py}], via disproportionation of the metal halide. Similarly, the reaction of the bis(imino)pyridine, 2,6-{ArNC(Me)}₂(NC₅H₃), bimpy, with “GaI” affords the salt [GaI₂(bimpy)][GaI₄]. Finally, the reaction of bis(2,6-diisopropylphenylimino)acenaphthene (ArBIAN) with “GaI” leads to a paramagnetic Ga(III) complex [GaI₂(ArBIAN)˙]. The X-ray crystal structures of all prepared complexes are reported.