本篇論文主要是研究低配位、低價數之雙核鎳金屬錯合物以及研究低配位之擴展的金屬鏈的合成(EMACs)。第一部分為雙核鎳錯合物， 有鑑於2009及2013年本實驗室成功利用苯上2,6位取代基為雙異丙基及苯上2,6位取代基為雙甲基的雙氮基脒配基合成出了[Ni(µ-κ2-HC(NDipp)2]2 (Dipp = 2,6-diisopropylphenyl)及[Ni(µ-κ2-HC(NDmp)2]2 (Dmp = 2,6-dimethylphenyl)，在此我們目標為合成以不對稱的雙氮基脒為配基的雙合鎳金屬錯合物，將取代基改為雙甲基和雙異丙基，合成出一系列的雙核鎳金屬錯合物。利用Li[HC(NDipp)(NDmp)]與2當量的碘化鎳反應可得到錯合物[Li(THF)4][Ni2I2(µ-I)2(µ-κ2-HC(NDipp)(NDmp))] (1) ; 而與0.5當量的碘化鎳反應可得到三片配基橋接在兩個鎳金屬上的雙鎳錯合物Ni2[(µ-κ2-HC(NDipp) (NDmp)]3 (3) 和 兩片配基橋接在一個鎳金屬上的單核鎳錯合物Ni[(κ2-HC(NDipp) (NDmp)]2 (4)。若將錯合物1與4當量的鉀石墨反應應可得到[Ni(THF)(µ-κ2-HC (NDipp)(NDmp)]2 (4)，錯合物5也可由1與1當量的Li[HC(NDipp)(NDmp)]與4當量的鉀石墨還原而得到，此法的產率會比錯合物1直接還原來得高。
第二部分為低配位之擴展的金屬鏈的研究，本實驗室成功的以2,6-bis(2,6-diisopropylphenyl)-4-methylpyridine為配基(簡稱N2NDipp)，合成出一系列多金屬中心錯合物。大部分的分子導線的例子都是以風車形結構為主，本實驗室合成2,7-bis(2,6-diisopropylphenyl)-1,8-naphthyridine配基(在此簡稱N2N2Dipp)，目標是想將配基的立體阻礙增加，想合成一系列低配位的多金屬錯合物。利用LiN2N2Dipp和兩當量的碘化銅反應可以得到錯合物Cu4[µ-κ4-(2,7-(NDipp)2-1,8-naphthyridine)]2 (6)；與兩當量的氯化鍺反應可以得到錯合物GeCl2[2,7-(HNDipp)2-1,8-naphthyridine]2 (8)；而與一當量的醋酸釕反應可以得到錯合物Ru4(THF)2(OAc)4[µ-κ4-(2,7-(NDipp)2-1,8-naphthyridine)]2 (9)。將錯合物9與兩當量的雙(三苯基正膦基)氯化銨(PPNCl)反應可以得到錯合物Ru2Cl4[μ-η2-2,7-(HNDipp)2-1,8-naphthyridine]2 (10)。

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.

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