本論文中，成功的合成且鑑定出一系列低配位的α-二亞胺基鈷與鎳金屬錯合物。在甲苯中以一當量的KC8還原(o,o’-iPr2C6H3-DAB)CoCl2 (o,o’-iPr2C6H3-DAB = 2.3-dimethyl-1,4-bis- (2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene)，可得到雙鈷錯合物[(o,o’-iPr2C6H3-DAB)Co(μ-Cl)]2 (1)；若改以兩當量還原，則得到半三明治式錯合物[(o,o’-iPr2C6H3-DAB)Co(η6-C7H8)] (2)；若使用乙醚或四氫呋喃做為溶劑還原(o,o’-R2C6H3-DAB)CoCl2 (R = iPr, Et)，可得到二聚體[(o,o’-R2C6H3-DAB)Co]2 (R = iPr (3), Et (4))。將錯合物2或3分別與白磷反應，皆可得到錯合物(μ-η4:η4-P4)[Co(o,o’-iPr2C6H3-DAB)]2 (5)，結構中磷原子形成平面結構以□4橋接兩個鈷金屬；而將錯合物2或3分別與硒元素反應，皆得到錯合物[(o,o’-iPr2C6H3-DAB)Co(μ-Se)]2 (6)，結構中硒原子橋接在兩個鈷金屬之間。
在甲苯中以兩當量的KC8還原(o,o’-iPr2C6H3-DAB)NiI2，可分離出反三明治式錯合物(μ-η3: η3-C7H8)[Ni(o,o’-iPr2C6H3-DAB)]2 (7)；若改用乙醚或四氫呋喃做為還原的溶劑，可得到具鎳-鎳鍵結構的錯合物[(o,o’-iPr2C6H3-DAB)Ni]2 (8)，其鎳-鎳鍵長為2.2946(8) A；以三當量KC8進行還原反應，則得到反三明治式錯合物(μ-η3: η3-C6H6)[Ni(o,o’-iPr2C6H3-DAB)]2(Et2O)2(THF)2 (9)。若以兩當量的KC8還原配基立障較小的□-二亞胺配基鎳錯合物(o,o’-Et2C6H3-DAB)NiI2，則是合成出逆磁性扭曲四面體的單核錯合物 [Ni(o,o’-Et2C6H3-DAB)2] (10)。
將錯合物8與白磷反應，得到四個磷原子橋接的雙核錯合物(μ-η4: η4-P4)[Ni(o,o’-iPr2C6H3-DAB)]2 (11)，這是一個與錯合物5類似的結構。與1,3,5,7-環辛四烯(簡寫為COT)反應，得到trans-(η2,2,η2,2- COT)[Ni(o,o’-iPr2C6H3-DAB)]2 (12)，結構中的1,3,5,7-環辛四烯分別以1,5及3,7位置的π鍵配位於兩個鎳金屬。二苯乙炔、苯乙炔以及苯甲腈與錯合物8反應後，會被還原成雙鍵，並配位在鎳金屬上，形成平面四方形的單核錯合物(η2-X)[Ni(o,o’-iPr2C6H3-DAB)] (X = PhCCPh (13), HCCPh (14), NCPh (15))。

In this thesis, a series of low-coordinate α-diimine cobalt and nickel complexes were successfully synthesized and characterized. Reduction of (o,o’-iPr2C6H3-DAB)CoCl2 (o,o’-iPr2C6H3-DAB = 2.3-dimethyl-1,4-bis- (2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene) by one equivalent of KC8 in toluene afforded a dicobalt complex [(o,o’-iPr2C6H3-DAB)Co(μ-Cl)]2 (1). However, when the amount of KC8 was increased from one to two equivalent, a half-sandwich complex [(o,o’-iPr2C6H3-DAB)Co(η6-C7H8)] (2) was generated. Interestingly, two dimeric complexes [(o,o’-R2C6H3-DAB)Co]2 (R = iPr (3), Et (4)) were isolated, if the reduction of (o,o’-R2C6H3-DAB)CoCl2 (R = iPr, Et) was carried out in ether or THF. Both 2 and 3 reacted with white phosphorus to lead to the isolation of a P4-bridged dicobalt complex (μ-η4: η4-P4)[Co(o,o’-iPr2C6H3-DAB)]2 (5), where the bridging square planar P4 coordinate to each cobalt atom in an □4 fashion. Furthermore, treatment of both complexes 2 and 3 with elemental selenium produced [(o,o’-iPr2C6H3-DAB)Co(μ-Se)]2 (6), in which two elemental selenium atoms bridge two cobalt atoms.
Reduction of (o,o’-iPr2C6H3-DAB)NiI2 by two equivalent of KC8 in toluene led to the isolation of an inverted-sandwich complex (μ-η3:η3-C7H8)[Ni(o,o’-iPr2C6H3-DAB)]2 (7). Interestingly, when the reduction was carried out in ether or THF, a Ni-Ni bonded complex [(o,o’-iPr2C6H3-DAB)Ni]2 (8) (Ni-Ni, 2.2946(8) A) was obtained. Notably, when the amount of KC8 was increased from two to three equivalent, an inverted-sandwich complex (μ-η3:η3-C6H6)[Ni(o,o’- iPr2C6H3-DAB)]2(Et2O)2(THF)2 (9) was obtained. Upon reduction of the less hindered (o,o’-Et2C6H3-DAB)NiI2 by two equivalent of KC8, a mononuclear distorted tetrahedral complex [Ni(o,o’-Et2C6H3-DAB)2] (10) was isolated.
Reaction of complex 8 with white phosphorus yielded a P4-bridged dinuclear complex (μ-η4:η4-P4)[Ni(o,o’-iPr2C6H3-DAB)]2 (11), in which the structure is similar to 5. Treatment of 8 with COT (COT = 1,3,5,7-cyclooctatetraene) yielded trans-(η2,2,η2,2-COT)[Ni(o,o’- iPr2C6H3-DAB)]2 (12), where COT coordinates to each nickel atom by 1,5 and 3,7 position π-bond. Diphenylacetylene, phenylacetylene and benzonitrile were reduced to double bond by 8 upon coordination to nickel atom forming mononuclear square planar complexes (η2-X)[Ni(o,o’-iPr2C6H3-DAB)] (X = PhCCPh (13), HCCPh (14), NCPh (15)).

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