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  • 學位論文

一. 雙鎳金屬雙氮基脒錯合物之反應性研究 二. 異核雙金屬錯合物合成之探討

1.Reactivity of Dinickel Amidinates 2.Pursuit of Heteronuclear Metal-Metal Bonded Complexes

指導教授 : 蔡易州

摘要


在本篇論文中第一部分,主要探討低配位、低價數雙鎳金屬錯合物的反應性,將[Ni(μ-HC(NDep)2)]2 (Dep = 2,6-diethylphenyl)與硫反應,發現硫原子會插入雙氮基脒配基中與氮原子鍵結,成為具有氮-硫鍵的新配基,得到產物(μ-S2)2{Ni[μ-HC(NDep)2(S)]}4 (1)。而將[Ni(μ-HC(NDep)2)]2與吡啶反應會形成{Ni[μ-HC(NDep)2](py)}2 (py = pyridine) (2);與氮氧化吡啶反應會形成{Ni[μ-HC(NDep)2](py-O)}2 (py-O = pyridine N-oxide) (3)。而我們更進一步的探討不同配基的雙鎳金屬錯合物[Ni(μ-HC(NDipp)2)]2 (Dipp = 2,6-diisopropylphenyl)、[Ni(μ-HC(NDep)2)]2、[(o,o’-Dipp-DAB)Ni]2 (o,o’-Dipp-DAB = 2,3-dimethyl-1,4-bis-(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene),與二乙基鋅的反應性,當[Ni(μ-HC(NDipp)2)]2與三當量的二乙基鋅反應會形成Ni(ZnEt)2[μ-HC(NDipp)2]2 (4);而將[Ni(μ-HC(NDep)2)]2與三當量的二乙基鋅反應會形成Ni2(ZnEt)2{[Ni(μ-HC(NDep)2)][Ni2(μ-HC(NDep)¬2)(ZnEt)2]}2 (5);最後使用[(o,o,-Dipp-DAB)Ni]2與四當量的二乙基鋅反應會形成(η2-C2H4)Ni(o,o,-Dipp-DAB) (6)。由這系列的化合物4、5和6中可以觀察到雙鎳金屬錯合物以立體障礙來控制與二乙基鋅的反應,形成了截然不同的產物,有形成鎳-鋅鍵、鎳-鋅團簇(Ni-Zn Clusters)、以及中心金屬鎳接上乙烯。 而在本文的第二部分,將探討異核雙金屬錯合物的研究,目前將MoCl3(THF)3與WCl3(DME)在80 °C下和兩當量的Li[HC(N-2,6-iPr2C6H3)¬2]反應得到Mo(Cl)2[μ-HC(NDipp)2]2¬ (7)、W2(μ-Cl)2(Cl)4[μ-HC(NDipp)2]2¬ (8),兩個中心金屬都為四價的產物,而同時也發現如果單純使用MoCl3(THF)3與兩當量Li[HC(N-2,6-Et2C6H3)¬2]反應可以得到Mo[Cl2(μ-Li(THF)2][μ-HC(NDep)2]2 (9),但是使用MoCl3(THF)3與兩當量立體障礙較大的Li[HC(N-2,6-iPr2C6H3)¬2] 與反應則會得到Mo2(μ-Cl)[Cl2Li(μ-THF)][μ-η2-HC(N-2,6-iPr2C6H3)2]2這個雙鉬金屬四重鍵錯合物。

並列摘要


In this thesis, we studied reactivity of low-coordinate and low-valent dinickel complexes. [Ni(μ-HC(NDep)2)]2 (Dep = 2,6-diethylphenyl) reacted with elemental sulfur to give the complex (μ-S2)2{Ni[μ-HC(NDep)2(S)]}4 (1). In this reaction, sulfur atoms inserted to Ni-N bonds to yield a new ligand contained nitrogen-sulfur bond. On the other hand, [Ni(μ-HC(NDep)2)]2 reacted with pyridine and pyridine N-oxide to furnish the complex {Ni[μ-HC(NDep)2](py)}2 (py = pyridine) (2) and {Ni[μ-HC(NDep)2](py-O)}2 (py-O = pyridine N-oxide) (3). Furthermore, the amidinate- and α-dimine-stabilized dinickel complexes [Ni(μ-HC(NDipp)2)]2 (Dipp = 2,6-diisopropylphenyl), [Ni(μ-HC(NDep)2)]2 and [(o,o’-Dipp-DAB)Ni]2 (o,o’-Dipp-DAB = 2,3-dimethyl-1,4-bis-(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene), showed interesting reactivity with diethyl zinc. The following mixed-metal complexes Ni(ZnEt)2[μ-HC(NDipp)2]2 (4), Ni2(ZnEt)2{[Ni(μ-HC(NDep)2)][Ni2(μ-HC(NDep)2)(ZnEt)2]}2 (5) and (η2-C2H4)Ni(o,o’-Dipp-DAB) (6) were isolated accordingly. The formation of these products was presumably controlled by steric hindrance of ligands. Complex 4 contained two Ni-Zn bonds. Complex 5 was a unique metal cluster contained 8 Ni and 6 Zn atoms. Complex 6 contained an ethylene group coordinated to the nickel center. In the second part, we tried to synthesize heteronuclear metal-metal bond complexes. At present, reaction of Li[HC(N-2,6-iPr2C6H3)¬2] with half of an equivalent of MoCl3(THF)3 and WCl3(DME) afforded Mo(Cl)2[μ-HC(NDipp)2]2¬ (7) and W2(μ-Cl)2(Cl)4[μ-HC(NDipp)2]2¬ (8). Both of the metal centers in these two complexes were tetravalent. On the other hand, reaction of Li[HC(N-2,6-Et2C6H3)¬2] and MoCl3(THF)3 gave the mononuclear complex Mo[Cl2(μ-Li(THF)2][μ-HC(NDep)2]2 (9). However, reaction of MoCl3(THF)3 with the more sterically hindered amidinate Li[HC(N-2,6-iPr2C6H3)¬2] gave the quadruply bonded complex Mo2(μ-Cl)[Cl2Li(μ-THF)][μ-η2-HC(N-2,6-iPr2C6H3)2]2.

參考文獻


(24) 李威廷 國立清華大學化學研究所碩士論文 2012
(36) 劉信呈國立清華大學化學研究所碩士論文 2010
(7) 張凱傑 國立清華大學化學研究所碩士論文 2009
(20) 顏君旭 國立清華大學化學研究所碩士論文 2009
(1) Laplaza, C. E.; Cummins, C. C. Science 1995, 268, 861.

被引用紀錄


林展民(2013)。雙鎢金屬多重鍵化合物之合成及其反應性研究〔碩士論文,國立清華大學〕。華藝線上圖書館。https://doi.org/10.6843%2fNTHU.2013.00389

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