本實驗室利用Li2[N2Ndipp] (N2Ndipp = 4-methyl-2,6-(N-2,6-iPr2C6H3)2 pyridine)為配基合成出雙核鍺一價化合物K2Ge2[N2Ndipp]2 (2)，將2與GeCl2‧dioxane和SnCl2反應，分別得到[GeCl]2Ge2[N2Ndipp]2 (3)與[SnCl]2Ge2[N2Ndipp]2 (4)。我們利用化合物2中具有高電荷密度的鍺(I)-鍺(I)金屬鍵與ZnI2反應，也成功合成出多金屬鏈化合物[ZnI]2Ge2[N2Ndipp]2(THF) (5)，有趣的是，其中心金屬鍺(I)-鍺(I)距離也從2.5168(6)Å縮短為2.4060(6)Å。當我們將2與由正己烷配成1M的GeCl4反應，可以得到V字形角錐狀的化合物 [GeCl2][GeCl]2[N2Ndipp]2 (8)，其GeCl4被還原成GeCl2並且以架橋的形式嵌入於鍺-鍺金屬鍵中間。另外，我們將3和4與KNCS反應，得到兩端鍺金屬上的Cl-離子由NCS-基團所取代的[GeNCS]2Ge2[N2Ndipp]2 (6)與[SnNCS]2Ge2[N2Ndipp]2 (7)。
有趣的是，當我們將3分別溶於冰正己烷或冰四氫呋喃溶劑中，並加入由正己烷配成1M的GeCl4反應，前者得到主要產物為鍺五員環 [(GeCl2)(GeCl)4][N2Ndipp]2 (9)，而後者其主要產物則為鍺四員環[GeCl]4[N2Ndipp]2 (10)，主要是由於受到溶劑效應(solvent effect)的影響所致。
我們將Li2[N2Ndipp]與CrCl2反應，合成出Cr2[N2Ndipp]2 (THF)2 (12)。本實驗室曾以Li2[N2Ndipp]與CrCl3反應後，再直接以KC8進行還原反應，可以分離出雙鉻(I)五重鍵金屬錯合物[(Et2O)KCr(N2Ndipp)]2 (11)，我們也能將12與KC8進行還原反應，發現可以得到高產率的11。當我們將11與CaI2反應，令人驚奇的是，成功合成出新穎的雙鉻(I)五重鍵Cr2Ca [N2Ndipp]2(THF)2 (15)，其鉻(I)-鉻(I)間距離為1.7356(7) Å，較11(1.7443(10) Å)縮短了約0.01 Å。另外，我們將11與AlMe3反應，得到三個鉻金屬原子以直線排列且不對稱的[μ-CH3]2Cr3[N2Ndipp]2 (THF) (16)，其鉻(II)-鉻(II)間距離分別為1.8989(6) Å與2.6283(6) Å。
其他嘗試中，我們首先利用Li[HC(NDipp)2] (NDipp = N-2,6- iPr2C6H3)配基與CrCl2得到Cr[HC(NDipp)2]2，接著加入GeCl2‧dioxane進行反應，成功合成出[(GeCl)(μ-Cl)Cr][HC(NDipp)2]2 (17)。之後，將17與還原劑LiAlH4進行反應，成功合成出具有鉻-鍺金屬鍵且新奇的 [(GeCl)(CrH)][HC(NDipp)2]2 (18)，其鉻(II)-鍺(II)鍵長為2.5610(16) Å。
以上所有合成出來的產物，皆已經過核磁共振光譜和元素分析鑑定。透過單晶X-ray繞射解析，我們也清楚了解其分子結構。

The low-valent and low-coordinate digermanium complex, K2Ge2[N2Ndipp]2 (2), was synthesize by the sterically hindered three-nitrogen donor ligand, Li2[N2Ndipp] (N2Ndipp = 4-methyl-2,6-(N-2,6-iPr2C6H3)2 pyridine). The bond length of Ge(I)-Ge(I) in 2 is 2.5168(6) Å. Treatment of 2 with GeCl2‧dioxane and SnCl2 gives two linear tetranuclear mixed-valence complexes, [MCl]2Ge2[N2Ndipp]2 (3: M = Ge; 4: M = Sn), respectively. These complexes 2, 3, and 4 are starting materials to synthesize the following low-coordinate multinuclear complexes.
Treatment of 2 with ZnI2 also produces a tetranuclear mixed-valence Zn(II)-Ge(I)-Ge(I)-Zn(II) complex, [ZnI]2Ge2[N2Ndipp]2(THF) (5), where the internal Ge(I)-Ge(I) bond length is significantly shortened to 2.4060(6)Å. Reaction of 2 with 1M stock solution of GeCl4 in hexane results in the formation of a inverted V-shape pyramidal trinuclear mixed-valence Ge(III)-Ge(II)-Ge(III) complex, [GeCl2][GeCl]2[N2Ndipp]2 (8), where GeCl4 is reduced to GeCl2 and bridges between two Ge(III) atoms.
Similar to molecular wire, reaction of 3 or 4 with KNCS undergoes SN2 reaction, giving tetranuclear complexes, [MNCS]2Ge2[N2Ndipp]2 (6: M = Ge; 7: M = Sn). Interestingly, due to the solvent effect, reaction of 3 and 1 equivalent of GeCl4 in n-hexane gave rise to the formation of cyclic pentanuclear germane, [(GeCl2)(GeCl)4][N2Ndipp]2 (9) as the major product. On the contrary, if this reaction is carried out in THF, cyclic tetranuclear germane, [GeCl]4[N2Ndipp]2 (10) is the major product instead.
Besides, treatment of Li2[N2Ndipp] with CrCl2 gives the complex Cr2[N2Ndipp]2(THF)2 (12). Upon reduction of 12 with KC8 leads to a quintuply-bonded complex, [(Et2O)KCr(N2Ndipp)]2 (11), which was already reported by our lab. Unfortunately, reaction of 11 with CaI2 failed to give a tetranuclear complex; instead it formed an amazing quintuply-bonded complex, Cr2Ca [N2Ndipp]2(THF)2 (15), where the Cr(I)-Cr(I) bond length is 1.7356(7) Å, shorter than 11, in which the Cr(I)-Cr(I) bond length is 1.7443(10) Å. Moreover, reaction of 11 with AlMe3 produces an asymmetric trichromium complex, [μ-CH3]2Cr3 [N2Ndipp]2(THF) (16). The Cr-Cr bond lengths are 1.8989(6) Å and 2.6283(6) Å, respectively.
In addition, the reaction of amidinate ligand, Li[HC(NDipp)2] (NDipp = N-2,6-iPr2C6H3) and CrCl2 produces the Cr[HC(NDipp)2]2. Treatment of the mixture of Cr[HC(NDipp)2]2 and GeCl2‧dioxane gives [(GeCl)(μ-Cl)Cr][HC(NDipp)2]2 (17). There is one chloride that bridges between germanium and chromium atoms. The addition of LiAlH4 to 17 leads to the isolation of heterodinuclear complex, [(GeCl)(CrH)][HC(NDipp)2]2 (18). The distance of Ge-Cr is 2.5610(16) Å and is assigned a single bond.
All the synthesized products have been characterized by NMR spectroscopy and elemental analysis, and their molecular structures have been determined by single crystal X-ray crystallography.

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