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。

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.

封面.......................................................I
中文摘要...................................................II
Abstract.................................................IV
謝誌......................................................ⅤI
目錄.....................................................VII
圖目錄.....................................................X
流程圖目錄.................................................XI

第一章 緒論.................................................1
1-1. 低配位低價數金屬錯合物...................................1
1-2. 雙核鎳金屬錯合物........................................4
1-3. 烷基鋅與過渡金屬反應.....................................8
1-4. 異核雙金屬錯合物.......................................10
第二章 低配位低價數雙鎳金屬錯合物反應性研究......................12
2-1. 前言.................................................12
2-2. 錯合物(μ-S2)2{Ni[μ-HC(NDep)2(S)]}4 (1)的合成與鑑定......12
2-3. 錯合物{Ni[μ-HC(NDep)2](Py)}2 (2)的合成與鑑定............15
2-4. 錯合物{Ni[μ-HC(NDep)2](py-O)}2 (3)的合成與鑑定..........17
第三章 低配位低價數雙鎳金屬錯合物與有機鋅化合物反應性研究...........20
3-1. 前言.................................................20
3-2. 錯合物Ni(ZnEt)2[μ-HC(NDipp)2]2 (4)的合成與鑑定..........24
3-3. 錯合物Ni2(ZnEt)2{[Ni(μ-HC(NDep)2)][Ni2(μ-HC(NDep)2) (ZnEt)2]}2 (5)的合成與鑑定..................................26
3-4. 錯合物(η2-C2H4)Ni(o,o，-Dipp-DAB) (6)的合成與鑑定.......30
3-5. 結論.................................................33
第四章 異核雙金屬錯合物研究...................................35
4-1. 前言.................................................35
4-2. 錯合物Mo(Cl)2[μ-HC(NDipp)2]2 (7)的合成與鑑定............36
4-3. 錯合物W2(μ-Cl)2(Cl)4[μ-HC(NDipp)2]2 (8)的合成與鑑定.....38
4-4. 結論.................................................40
第五章 雙核鉬金屬多重鍵合成研究................................41
5-1. 前言.................................................41
5-2. 錯合物Mo[Cl2(μ-Li(THF)2][μ-HC(NDep)2]2 (9)的合成與鑑定..43
5-3. 結論.................................................46
第六章 實驗步驟.............................................47
6-1. 實驗使用儀器以及一般操作.................................47
6-2. 實驗使用藥品及溶劑......................................48
6-3. 實驗步驟..............................................49
6-3-1. 錯合物(μ-S2)2{Ni[μ-HC(NDep)2(S)]}4 (1)的合成 [As3-48] ..........................................................49
6-3-2. 錯合物{Ni[μ-HC(NDep)2(py)]}2 (2)的合成 [As3-106].....49
6-3-3. 錯合物{Ni[μ-HC(NDep)2](py-O)}2 (3)的合成 [As2-240]...50
6-3-4. 錯合物Ni(ZnEt)2[μ-HC(NDipp)2]2 (4)的合成 [As3-50]....51
6-3-5. 錯合物Ni2(ZnEt)2{[Ni(μ-HC(NDep)2)][Ni2(μ-HC(NDep)2) (ZnEt)2]}2 (5)的合成[As3-90]...............................52
6-3-6. 錯合物(η2-C2H4)Ni(o,o’-Dipp-DAB) (6)的合成 [As1-89]..53
6-3-7. 錯合物Mo(Cl)2[μ-HC(NDipp)2]2 (7)的合成 [As3-30H].....54
6-3-8. 錯合物W2(μ-Cl)2(Cl)4[μ-HC(NDipp)2]2 (8)的合成[As3-30-THF]......................................................55
6-3-9. 錯合物Mo[Cl2(μ-Li(THF)2][μ-HC(NDep)2]2 (9)的合成 [As2-214]......................................................56
第七章 其他嘗試與晶體結構資料..................................57
7-1. 其他嘗試..............................................57
7-1-1. [(o,o，-Dipp-DAB)Co(η6-C7H8)]與二乙基鋅(Diethylzinc)反應 .........................................................57
7-1-2. [(o,o，-Dipp-DAB)Ni]2與二苯基鋅(Diphenylzinc)反應....57
7-1-3. [(o,o，-Dipp-DAB)Co]2與二乙基鋅(Diethylzinc)反應.....58
7-1-4. [(o,o，-Dipp-DAB)Ni]2與As[μ-(CH2PPh2)2]+I-反應......58
7-1-5. [(o,o，-Dipp-DAB)Co(η6-C7H8)]與As[μ-(CH2PPh2)2]+I-反應 .........................................................59
7-1-6. [(o,o，-Dipp-DAB)Co(η6-C7H8)]與二苯基鋅(Diphenylznic)反應........................................................59
7-1-7. [(o,o，-Dipp-DAB)Co]2與As[μ-(CH2PPh2)2]+I-反應......60
7-1-8. [(o,o，-Dipp-DAB)Ni]2與二甲基鋅(Dimethylzinc)反應....60
7-1-9. [(o,o，-Dipp-DAB)Ni]2與P[μ-(CH2PPh2)2]+I-反應.......61
7-1-10. [(o,o，-Dipp-DAB)Ni]2與Phenylsilane (PhSiH3)反應...62
7-1-11. [(o,o’-Dipp-DAB)Ni]2與Diphenylgermane (Ph2GeH2)反應 ..........................................................62
7-1-12. [(o,o，-Dipp-DAB)Ni]2與異氰酸苯酯(Phenylisocyanate )反應........................................................63
7-1-13. [(o,o’-Dipp-DAB)Co(η6-C7H8)]與二甲基鋅(Dimetnylznic)反應........................................................64
7-1-14. [(o,o，-Dipp-DAB)Co(η6-C7H8)]與異氰酸苯酯(Phenylisocyanate)反應....................................64
7-1-15. [[Ni(μ-HC(NDep)2)]2與異氰酸苯酯(Phenylisocyanate)反應 ..........................................................65
7-1-16. [[Ni(μ-HC(NDep)2)]2與二甲基鋅(Dimethylzinc)反應.....66
7-1-17. [(o,o’-Dipp-DAB)Ni]2與三甲基鋁(Trimethylaluminium)反應 .........................................................66
7-1-18[Ni(μ-HC(NDep)2)]2與二苯基鋅(Diphenylzinc)反應........67
7-1-19. [(o,o’-Dipp-DAB)Co(η6-C7H8)]與吡啶(Pyridine)反應...67
7-1-20. [(o,o’-Dipp-DAB)Co(η6-C7H8)] 與三甲基鋁反應.........68
7-1-21[Ni(μ-HC(NDep)2)]2與噠嗪(Pyrdazine)反應..............68
7-1-22[Ni(μ-HC(NDep)2)]2與白磷(P4)反應.....................69
7-1-23[Ni(μ-HC(NDep)2)]2與硒(Se)反應.......................70
7-1-24. [Ni(μ-HC(NDep)2)]2與三甲基鋁反應....................71
7-1-25. [Ni(μ-HC(NDep)2)]2與Ni(COD)2反應...................71
7-1-26. Mo(Cl)2[μ-HC(NDipp)2]2的還原反應..................72
7-1-27. Mo(Cl)2[μ-HC(NDipp)2]2與Bis(benzene)chromium反應...72
7-1-28. MoCl3(THF)3、CrCl3與去質子化的雙氮基脒配基反應.........73
7-1-29. [Ni(μ-HC(NDep)2)]2與二乙基鋅反應....................74
7-1-30. [Ni(μ-HC(NDipp)2)]2與二乙基鋅反應...................75
7-2. 晶體結構資料表.........................................77
7-2-1. (μ-S2)2{Ni[μ-HC(NDep)2(S)]}4 (1)的晶體資料..........77
7-2-2. {Ni[μ-HC(NDep)2(py)]}2 (2)的晶體資料................78
7-2-3. 錯合物{Ni[μ-HC(NDep)2](py-O)}2 (3)的晶體資料.........79
7-2-4. 錯合物Ni(ZnEt)2[μ-HC(NDipp)2]2 (4)的晶體資料.........80
7-2-5. 錯合物Ni2(ZnEt)2{[Ni(μ-HC(NDep)2)][Ni2(μ-HC(NDep)2) (ZnEt)2]}2 (5)的晶體資料...................................81
7-2-6. 錯合物(η2-C2H4)Ni(o,o’-Dipp-DAB) (6)的晶體資料.......82
7-2-7. 錯合物Mo(Cl)2[μ-HC(NDipp)2]2 (7)的晶體資料...........83
7-2-8. 錯合物W2(μ-Cl)2(Cl)4[μ-HC(NDipp)2]2 (8)的晶體資料....84
7-2-9. 錯合物Mo[Cl2(μ-Li(THF)2][μ-HC(NDep)2]2 (9)的晶體資料.85
參考文獻..................................................86

(1) Laplaza, C. E.; Cummins, C. C. Science 1995, 268, 861.
(2) Johnson, L. K.; Killian, C. M.; Brookhart , M. J. Am. Chem. Soc. 1995, 117, 6414.
(3) Nakao, Y.; Yamada, Y.; Hiyama, T. J. Am. Chem. Soc. 2010, 132, 39.
(4) Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144.
(5) 林亨菕 國立清華大學化學研究所碩士論文 2011
(6) Jones, C.; Schulten, C.; Fohlmeister, L.; Stasch, A.; Murray, K. S.; Moubaraki, B.; Kohl, S.; Ertem, M. Z.; Gagliardi, L.; Cramer, C. J. Chem. Eur. J. 2011, 17, 1294.
(7) 張凱傑 國立清華大學化學研究所碩士論文 2009
(8) Bollermann, T.; Christian, G.; Fisher, R. A. Coord. Chem. Rev. 2012, 256, 537.
(9) Crotty, D. E.; Anderson, T. J.; Glick, M. D.; Oliver, J. P. Inorg. Chem. 1977, 16, 2346.
(10) Budzelaar, P. H. M.; Van Der Zeijden, A. H.; Boersma, J.; Van Der Kerk, G. J. M.; Spek, A. L.; Duisenberg, A. J. M. Organometallics 1984, 3, 159.
(11) Ohashi, M.; Matsubara, K.; Suzuki, H. Organometallics 2007, 26, 2330.
(12) Garner, C. D.; Senior, R. G. J. Chem. Soc., Chem. Commun. 1974, 597, 580.
(13) Hoxmeier, R. J.; McCarley, R. E.; Katovit, V.; Templeton, J. L. J. Am. Chem. Soc. 1975, 97, 5300.
(14) 黃哲偉 國立清華大學化學研究所碩士論文 2011
(15) Cummins, C. C. Chem. Commun. 1998, 17, 1777.
(16) Tran, B. L.; Thompson, R.; Ghosh, S.; Gao, X. F.; Chen, C. H.; Balk, M. H.; Mindiola, D. J. Chem. Commun. 2013, 49, 2768.
(17) Baker, M. V.; Field, L. D.; Hambley, T. W. Inorg. Chem. 1988, 27, 7.
(18) Evans, D. F.; J. Chem. Soc. 1959, 2003.
(19) Schubert, E. M. J. Chem. Educ. 1992, 69, 62.
(20) 顏君旭 國立清華大學化學研究所碩士論文 2009
(21) Resa, I.; Carmona, E.; Gutierrez-Puebla, E.; Monge, P. Science 2004, 8, 1136.
(22) Budzelaar, P. H. M.; Boersma, J.; Van Der Kerk, G. J. M.; Spek, A. L.; Duisenberg, A. J. M. Organometallics 1985, 4, 680.
(23) Studemann, T.; Ibrahim-Ouali, M.; Knochel, P. Tetrahedron 1998, 54, 1299.
(24) 李威廷 國立清華大學化學研究所碩士論文 2012
(25) Grirrane, A.; Resa, I.; Rodrıguez, A.; Carmona, E. Coord. Chem. Rev. 2008, 252, 1532.
(26) Balch, A. L.; Holm, R. H. J. Am. Chem. Soc. 1966, 88, 5201.
(27) Sgro, M. J.; Stephan, D. W. Dalton Trans. 2010, 39, 5745.
(28) Hsu, C.-H.; Yu, J.-S. K.; Yen, C.-H.; Lee, G.-H.; Wang, Y.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2008, 47, 9933.
(29) Tsai, Y.-C.; Chen, H.-Z.; Chang, C.-C.; Yu, J.-S. K.; Lee, G.-H.; Wang, Y.; Kuo, T.-S. J. Am. Chem. Soc. 2009, 131, 12534.
(30) Huang, Y.-L.; Lu, D.-Y.; Yu, H.-C.; Yu, J.-S. K.; Hsu, C.-W. Angew. Chem Int. Ed. 2012, 51, 7781.
(31) Chen, H.-Z.; Liu, S.-C. Yen, C.-H.; Yu, J.-S. K.; Shieh, Y.-J.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2012, 51, 10342.
(32) Wu, P.-F.; Liu, S.-C.; Shieh, Y.-J.; Kuo, T.-S.; Lee, G.-H.; Wang, Y.; Tsai, Y.-C. Chem. Commun. 2013, 49, 4391.
(33) Nippe, M.; Timmer, G. H.; Berry, J. F. Chem. Commun. 2009, 29, 4357.
(34) Liu, S.-C.; Ke, W.-L.; Yu, J.-S. K.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2012, 51, 6394.
(35) Hsu, C.-W.; Yu, J.-S. K.; Yen, C.-H.; Lee, G.-H.; Wang, Y.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2008, 47, 9933.
(36) 劉信呈國立清華大學化學研究所碩士論文 2010