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

The reaction of [Ge{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (1) with LiBut or LiC equivalent to CPh in Et2O afforded substituted products [Ge(R){N(SiMe3C(Ph)C(SiMe3)(C5H4N-2)}] [R) But (2) or CtCPh (3)], respectively. However, the one-pot reaction of 1 with PhC equivalent to CH and (BuLi)-Li-n in Et2O afforded lithium germinate [{(PhC equivalent to C)(3)Ge}(3)GeLi(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.