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

GaI reacts with 2,2'-bipyridine (bipy) to give salts of composition [Ga(bipy)(3)][I](3), [{(bipy)(2)Ga}(2)(mu-OH)(2)](2)[Ga2I6][I](6) or [{(bipy)(2)Ga}(2)(mu-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 RN=C(H)Py, Py = 2-pyridyl, R = Ar (C6H3Pr2i-2,6) or Bu-t, a reductive coupling of the C=N functionality occurs to give the diamido-digallium(III) complexes [{I2Ga[eta(2)-(Py)(NR)C(H)]}(2)], In contrast, InCl reacts with ArN=C(H)Py to give an adduct, [InCl3(THF) {eta(2)-ArN=C(H)Py}], via disproportionation of the metal halide. Similarly, the reaction of the bis(imino)pyridine, 2,6-(ArN=C(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.