以含氮雜環碳烯咔唑配位基與金屬之醋酸或鹵素衍生物經由錯化反應可以得到一系列pincer-type 含氮雜環碳烯(N-hetereocyclic carbene)咔唑金屬錯化合物。此類金屬錯化合物會因其金屬不同而造成配位型態不同。
其中鈷金屬錯化合物 (4e-6e) 的固態分子結構由X-ray 單晶體繞射分析知此錯化合物為六配位’Co(III)’雙配位基結構。另外鎳金屬錯化合物由X-ray 單晶繞射得知為四配位Ni(II)單配位基結構 (4b-6b,4c-6c) 。銅金屬錯化合物 (4d-6d)以質譜儀分析推測可能結構為類似鎳金屬錯化合物之四配位Cu(II)結構。

在化性方面，鎳金屬錯化合物 (4a-6a) 在氧氣下與氰基烷和鹼基反應，經由氰基烷之C-CN 斷鍵可形成氰基鎳金屬錯化合物 (4f-6f)。經由反應機制探討，推測鹼基應先與氰基烷進行去質子化再與氧氣以及鎳金屬進行斷鍵反應。氣相層\析質譜儀以及氣相層析儀分析其氰基烷斷鍵後之產物，其中雙聚物的出現可發現在此反應中會涉及到碳與碳的成鍵與斷鍵作用。在物性方面，銅與配位基的鍵結會增強配位基在373nm的放光效應。

A series of cobalt, nickel and copper 1,8-bis(imidazol-1-yl) carbazolide compoundswere prepared by complexation of 1,8-bis(imidazol-1-yl) carbazolide ligands with metal acetates or halides. Their molecular structures strongly depend on the central metal atoms. By X-ray diffraction crystallography analysis, the cobalt atom in the complexes exhibits a six-coordinated octahedral geometry, in which two 1,8-bis(imidazol-1-yl) carbazolide ligands attach to the Co(III) ion with two N atoms of the carbazole in cis position. On the other hand, the nickel complexes possess a twisted square planar geometry for the central Ni (II) ion. Moreover, the cobalt and nickel complexes have been fully characterized by 1H NMR, 13C NMR, EA, MASS.According to the analysis of MASS, the copper derivatives might have the molecular structures to similar to the nickel analogs.

The Nickel 1,8-bis(imidazol-1-yl)carbazolide complexes may react with alkylnitrile under basic and aerobic.Condition to form nickel cyanide complexes. The study of the mechanism of this reaction show that deprotonation of alkylnitrile would be the first step of the reaction. The observation of benzil indicates that both C-C bond breaking and formation would occur during the reaction. Optical study also shows the metal complexation would enhance the efficiency of the photoluminescence of 1,8-bis(imidazol-1-yl)carbazolide in the cases of copper complexes.

中文摘要…………………………………………………………………1
英文摘要…………………………………………………………………3
第一章 緒論
1.1 前言…………………………………………………………………5
1.2 研究動機…………………………………………………………19
第二章 鈷､鎳及銅金屬錯化合物合成與反應性之研究
2.1 鎳金屬錯化合物之合成…………………………………………20
2.1.1 溴-鎳金屬錯化合物之合成與鑑定……………………………22
2.1.2 氯-鎳金屬錯化合物之合成與鑑定……………………………30
2.2 鈷金屬錯化合物之合成與鑑定…………………………………37
2.3 銅金屬錯化合物之合成與鑑定…………………………………44
2.4 結論………………………………………………………………48
第三章 鎳金屬錯化合物與氰基烷之反應性探討
3.1 研究動機…………………………………………………………50
3.2 鎳金屬錯化合物與氰基烷之斷鍵反應機制探討
3.2.1 氰基烷､鹼基以及鎳金屬錯化合物反應順序探討…………53
v
3.2.2 鹼基當量數以及斷鍵後之有機產物探討……………………55
3.2.3 探討斷鍵機制可能路徑………………………………………60
3.2.4 斷鍵反應之延伸探討…………………………………………62
3.2.5 以不同鹼基以及溶劑延伸探討斷鍵反應……………………66
3.3 結論及未來展望…………………………………………………69
第四章 實驗步驟與方法
4.1 一般實驗…………………………………………………………71
4.2 重要分析儀器之型號……………………………………………71
4.3 實驗步驟
3,6-di-tert-butylcarbazole (1)…………………………………73
3,6-di-tert-butyl-1,8-dibromocarbazole (2)..............73
3,6-di-tert-butyl-1,8-bis(imidazol-1-ol)carbazole (3)……74
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium-1-yl)carbazole diiodide (4) (L-Me-I)…………………………………75
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium-1-yl)carbazole dibromide (5) (L-butyl-Br)…………………………………………………………………………74
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium-1-yl)carbazole dibromide
(6) (L-benzyl-Br)……………………………………………………75
vi
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Ni-OAc (4a)
(Ni-Me-OAc)…………………………………………………………76
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Ni-OAc (5a)
(Ni-butyl-OAc)………………………………………………………77
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Ni-OAc (6a)
(Ni-benzyl-OAc)………………………………………………………78
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Ni-CN (4f)
(Ni-Me-CN)……………………………………………………………79
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Ni-CN (5f)
(Ni-butyl-CN)…………………………………………………………80
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Ni-CN (6f)
(Ni-benzyl-CN)………………………………………………………81
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Ni-Cl (4c)
(Ni-Me-Cl)……………………………………………………………83
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Ni-Cl (5c)
(Ni-butyl-Cl)…………………………………………………………84
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Ni- Cl (6c)
(Ni-benzyl-Cl)………………………………………………………85
vii
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Ni-Br (4b)
(Ni-Me-Br)……………………………………………………………86
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Ni- Br (5b)
(Ni-butyl-Br)…………………………………………………………87
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Ni- Br (6b)
(Ni-benzyl-Br)………………………………………………………87
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Co-I (4e)
(Co-Me-I)………………………………………………………………88
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Co-Br (5e)
(Co-butyl-Br)…………………………………………………………88
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Co-Br (6e)
(Co-benzyl-Br)………………………………………………………90
3,6-di-tert-butyl-1,8-bis(3-methylimidazolium)carbazolide-Cu-Cl (4d)
(Cu-Me-Cl)……………………………………………………………91
3,6-di-tert-butyl-1,8-bis(3-butylimidazolium)carbazolide-Cu-Cl (5d)
(Cu-butyl- Cl)………………………………………………………92
3,6-di-tert-butyl-1,8-bis(3-benzylimidazolium)carbazolide-Cu-Cl (6d)
(Cu-benzyl- Cl)………………………………………………………92
viii
探討鎳金屬錯化合物與氰基烷之實驗條件
鹼基當量數探討………………………………………………………93
以氫氧化鉀做鹼基探討實驗條件……………………………………94
鎳金屬錯化合物置換鹵素反應………………………………………94
第五章 參考文獻………………………………………………………96
附錄一 質譜圖………………………………………………………101
附錄二 藥品廠牌……………………………………………………111
附錄三 x-ray data…………………………………………………113
ix
表目錄
表1. 第10､11､12 過渡族金屬價格 ...................................................... 11
表2. 以4A 置換溴官能基條件測試 ......................................................... 24
表 3. 4A 與溴化鈉實驗條件...................................................................... 26
表4. 4B-6B､4A-6A 核磁共振位移 ........................................................... 27
表5. 溴-鎳金屬錯化合物質譜分子量表 .................................................. 29
表6. 合成氯-鎳金屬錯化合物條件測試 .................................................. 31
表7. 氯根鎳金屬錯化合物核磁共振位移 ................................................ 32
表8. BOND LENGTHS [Å] AND ANGLES [°] FOR NI-BUTYL-CL ( 5C ) ............. 34
表9. BOND LENGTHS [Å] AND ANGLES [°] FOR NI-METHYL-CL ( 4C ) .......... 36
表10. 與醋酸鈷在60℃以及室溫下反應訊號消長積分比 ....................... 42
表11. 銅金屬錯化合物質譜分子量表 ....................................................... 45
表12. 斷鍵初步條件探討 ........................................................................... 52
表13. 反應順序探討條件 ........................................................................... 53
表14. 反應機制鹼基當量測試條件 ........................................................... 57
表15. 反應機制探討有機成分質譜分析結果 ........................................... 58
表16. 不同鎳金屬錯化合物斷鍵反應結果 ............................................... 62
表17. 路易士酸鹼對斷鍵產物之反應性 ................................................... 65
x
圖目錄
圖1. 釕金屬錯化合物 ................................................................................. 5
圖2. 以釕金屬錯化合物進行環庚烯開環聚合催化 .................................. 6
圖3. 鈀金屬錯化合物 ................................................................................. 6
圖4. ARDUENGO 首先分離出之含氮雜環碳烯 ........................................... 7
圖5. TOLMAN ELECTRONIC PARAMETERS 比較圖 ......................................... 8
圖6. 高氧化態鎳金屬中心 ......................................................................... 9
圖7. 高氧化態金屬錯化合物 ..................................................................... 9
圖8. 含氮雜環碳烯鈀金屬錯化合物應用於AEROBIC CONDITION REACTION
.............................................................................................................. 10
圖9. 以金金屬錯化合物將炔類氧化成酮 ................................................ 10
圖10. 鈷金屬錯化合物與氧分子反應式..................10
圖11. 鎳金屬錯化合物與氧分子反應式 ................................................... 11
圖12. 鈷金屬錯化合物示意圖 ................................................................... 13
圖13. Danopoulos 團隊合成之鈷金屬錯化合物............13
圖14. INAMOTO 團隊發表之鎳金屬錯化合物 .......................................... 14
圖15. 應用於SUZUKI-MIYAURA REACTION 之鎳金屬錯化合物 ................. 15
圖16. 銅金屬錯化合物之應用性 ............................................................... 15
圖17. [(SIMES)2CU][CU(CF3)2] 晶體結構 .............................................. 16
圖18. 銅金屬錯化合物結構圖 ................................................................... 17
圖19. 銠金屬錯化合物結構圖 ................................................................... 18
圖20. Kunz 團隊合成出之銠金屬錯化合物晶體結構R…………………..18
圖21. 配位基與鎳金屬錯化合物合成策略 ............................................... 21
圖 22. 以6 當量三乙基胺進行化合物5A 之合成 ..................................... 22
xi
圖 23. 以6 當量三乙基胺進行化合物5 之混合物核磁共振光譜圖 ........ 23
圖24. 鹵素置換反應式 .............................................................................. 24
圖25. 4A 與溴化鈉水溶液反應圖譜 ........................................................ 25
圖 26. 溴-鎳金屬錯化合物分子結構圖 ..................................................... 29
圖27. 氯-鎳金屬錯化合物合成反應式 ...................................................... 30
圖28. NI-BUTYL-CL (5C )晶體結構 ............................................................ 33
圖29. ONG 團隊之MONO &BIS N-HETEREOCYCLIC CARBENE 鎳金屬錯化合物
結構 ...................................................................................................... 34
圖30. NI-METHYL-CL ( 4C )晶體結構 ........................................................ 35
圖31. 鈷金屬錯化合物合成反應式 ........................................................... 37
圖32. 雙配位基鈷金屬錯化合物合成反應式 ........................................... 38
圖33. 鈷金屬錯化合紫外可見光光譜圖 (A)化合物6 與6E 疊圖(B)化合物
5 與5E 疊圖(C)化合物4 與4E 疊圖(D)化合物4E､5E､6E 疊圖(10-5
M IN CH3CN) .................................................................................... 40
圖34. 4 與醋酸鈷60℃下反應結果 ......................................................... 42
圖35. 4 與醋酸鈷室溫下反應結果 .......................................................... 42
圖36. 單配位基鈷金屬錯化合物紫外光光譜圖 ........................................ 43
圖37. 單配位基鈷金屬錯化合物可能結構 ............................................... 43
圖41. 銅金屬錯化合物結構推測圖 ........................................................... 45
圖38. 銅金屬錯化合物與配位基之紫外光光譜疊圖(10-5M IN CH3CN) ... 46
圖39. 銅金屬錯化合物4D､5D､6D (1.3X10-5M IN CH3CN )PL 疊圖 ....... 47
圖40. 銅金屬錯化合物4D､5D､6D 與配位基4､5､6(1.3X10-5M IN
CH3CN)PL 疊圖 ............................................................................... 47
xii
圖42. 氰基烷與鎳金屬錯化合物反應式 ................................................... 50
圖43. -ALLYL NICKEL NHC COMPLEXES 製備以及氧化作用 ..................... 50
圖44. RADIUS 團隊發表之斷氰鍵反應 ....................................................... 51
圖45. LIU 團隊發表之斷氰鍵反應 ............................................................. 51
圖46. GC-MS 分析有機相圖譜 .................................................................. 55
圖47. 相層析儀分析有機層圖譜 ............................................................... 56
圖48. 乙腈與正丁基鋰反應顏色變化。(A)尚未加入正丁基鋰(B)(C)加入一
當量正丁基鋰(D)加入兩當量正基鋰(E)加入氧氣 .......................... 57
圖49. 反應順序測試 .................................................................................. 60
圖50. 推測斷鍵可能機制 ........................................................................... 61
圖51. NI(DPPF)BET3 金屬錯化合物 ............................................................. 64
圖52. [4A：氫氧化鉀：氰基烷]=[1:10:20]反應一天實驗結果 ................. 66
圖53. [4A：氫氧化鉀：氰基烷]=[1:10:20]反應兩天實驗結果 ............... 67

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