Reactivity of Pyridyl-1-azaallyl Germanium(II) Chloride: Synthesis of Novel Lithium Germinate [{(PhC⋮C)₃Ge}₃GeLi(Et₂O)₃] and Ge(II)−M(I) (M = Cu and Au) Adducts

Abstract

The reaction of [Ge{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (1) with LiBut or LiC⋮CPh in Et2O afforded substituted products [Ge(R){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}] [R = But (2) or C⋮CPh (3)], respectively. However, the one-pot reaction of 1 with PhC⋮CH and BunLi in Et2O afforded lithium germinate [{(PhC⋮C)3Ge}3GeLi(Et2O)3] (4). Compound 1 can also undergo ligand transfer reaction with LiAlH4 to give [AlH{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}2] (5). Treatment of 1 with excess NaBH4 in THF afforded germanium(II) hydride-borane adduct [Ge(BH3){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}H] (6). The reaction of 1 with MI (M = Cu and Au) gave the first examples of Ge(II)−M(I) adducts [Ge(CuI){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl]4 (7) and [Ge(AuI){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (8). Compounds 2−8 have been characterized by X-ray analysis.