Abstract
Treatment of the lithiated amidinato ligand Li[HC(NDipp)(NDmp)] (Dipp = 2,6-diisopropylphenyl, Dmp = 2,6-dimethylphenyl) with 2 equiv of NiI2 afforded the dinickel complex [Li(THF)4][Ni2I2(µ-I)2(µ-κ2-HC(NDipp)(NDmp))] (1). However, reaction of the lithiated amidinate Li[HC(NDmp)2] ligand with 0.5 equiv of NiI2 resulted in the formation of the lantern-type dinuclear complex, Ni2[µ-κ2-HC(NDipp)(NDmp)]3 (3) and the mononuclear complex Ni[κ2-HC(NDipp)(NDmp)]2 (4). Subsequent KC8 reduction of 1 resulted in the isolation of the dinickel bisamidinate compound [Ni(THF)(µ-κ2-HC(NDipp)(NDmp)]2 (5). Compound 5 can be alternatively prepared from the reaction of 1 with 1 equiv of Li[HC(NDipp)(NDmp)] followed by 4 equiv of KC8. The latter route produced 5 with a better yield. In the second part, we focused on the study of extended metal atom chains (EMACs). Treatment of the Li[N2N2Dipp] (N2N2=2,7-bis(2,6-diisopropylphenyl)-1,8-naphthyridine) with 2 equiv of CuI afforded the tetracopper complex Cu4[µ-κ4-(2,7-(NDipp)2-1,8-naphthyridine)]2 (6). However, reaction of the Li[N2N2Dipp] with 2 equiv of GeCl2∙dioxane afforded the digermanium complex GeCl2[2,7-(HNDipp)2-1,8-naphthyridine]2 (8), where the amido groups were protonated. Addition of the Li[N2N2Dipp] to 1 equiv of Ru(OAc)4Cl produced the tetraruthenium complex Ru4(THF)2(OAc)4[µ-κ4-(2,7-(NDipp)2-1,8-naphthyridine)]2 (9). Subsequent addition of 2 equiv of [PPN]Cl to 9 led to the formation of the diruthenium complex Ru2Cl4[μ-η2-2,7-(HNDipp)2-1,8-naphthyridine]2 (10), where the amido groups were protonated as well.