雙原子配位基 ( CO、NO、CN ) 在生物體為重要的配位基，本論文乃透過中心金屬鈷合成類似三配位基在同一金屬上的四配位錯合物，當錯合物在接上配位基時，鈷化合物的雙原子分子改變環境產生π-acceptor 和 
σ-donor 變化，並透過紅外線光譜儀探究其振動能量及 X-ray 單晶繞射儀鑑定鈷化合物結構。
化合物 [(NO)Fe(N2S2)Fe(NO)2]+ 化合物 
(N2S2= N,N’-bis(2-mer- capt-oethyl)-1,4-diazacycloheptane) 在 2014 被發表，可當作還原質子 (H+) 產生氫氣 (H2) 的電催化劑，本篇論文以 
P2S2= meso-1,3Bis[(mercaptoethyl)phenylphosphino] propane (H2meppp) 做為配位基，且比較P與N做配位時，特性與穩定度的不同以求改良並藉由紅外線光譜探討其配位方式。
嘗試對 [(NO)Fe(N2S2)Fe(NO)2]+ 化合物做改良與穩定催化性測試，將氧化石墨烯固定在自製的金電極表面上，用於電催化產氫實驗，跟直接加入氧化石墨烯液體在原系統中觀察催化反應時氧化石墨烯是否影響催化性。

Diatomic ligand (CO, NO, CN) are very important lignds in coordination chemistry. All of them are common used in biological enzymes. They are binding on metal as a π-acceptor and a σ-donor. We design new complexes with three different diatom ligands in one cobalt coordinated center. It will provide a new point of view to explain π-acceptor and σ-donor when three diatomic ligands bind to one metal center.
The hydrogenases is a redox active enzyme for the interconversion of proton and hydrogen in a biological system. The chemical structure of          [FeFe]-hydrogenase contains iron centers, bridging dithiolate and diatomic CO/CN- ligands on the iron centers.  In 2014, we reported the cationic complex [(NO)Fe(N2S2)Fe(NO)2]+ and neutral [(NO)Fe(N2S2)Fe(NO)2] 
( N2S2=N, N-bis(2-mercaptoethyl)-1,4-diazacycloheptane ) can be the biomimetic functional model for [FeFe]-hydrogenase. The conversion of strong (HBF4) and weak (CH3COOH) acid to the hydrogen can be achieved by one and two electron reduction, respectively. In this study, we will also synthesize the iron complexes analog and modify the N2S2 ligand to the 
P2S2( meso-1,3 Bis[(mercaptoethyl)phenylphosphino] ) ligand.
We attempted to test [(NO)Fe(N2S2)Fe(NO)2]+ catalytic efficiency with graphene oxide. Firstly, we make a gold electrode adsorbed graphene oxide and it can be used to electrocatalytic hydrogen reaction. Secondly, we inject graphene oxide solution to original system and compare the differences of stability and properties.
Keywords: nitrosyl iron complexes, π-accepting, graphene oxide, hydrogenase

內容目錄
第一章 緒論	1
1.1	前言	1
1.2	配位鍵	2
1.3	雙原子配位基分子特性	3
1.4	磷配位 (PR3) 與氮異環碳烯 (N-Heterocyclic Carbenes)	4
1.5	氫化酶	7
1.6	含磷硫配位基	9
1.7	亞硝基配位 (nitrosyl)	10
1.8	氧化石墨烯 ( graphene oxide, GO )	12
1.9	研究動機	13
第二章 實驗部分	16
2.1 實驗方法	16
2.2 實驗溶劑與藥品	16
2.3 實驗儀器	19
2.4. 化合物合成	20
2.4.1合成1,3-Dimethyl-2,3-dihydro-1H-imidazole (NHC-Me)	20
2.4.2合成(CO)3Co(NO)	20
2.4.3合成 (NHC-Me)(CO)2Co(NO) (1)	21
2.4.4合成(NHC-iMes)(CO)2Co(NO) (2)	22
2.4.5合成P(Cy)3(CO)2Co(NO) (3)	23
2.4.6合成P(Bu)3(CO)2Co(NO) (4)	23
2.4.7合成P(Ph)3(CO)2Co(NO) (5)	24
2.4.8合成P(OEt)3(CO)2Co(NO) (6)	25
2.4.9合成[P(Cy)3Co(NO)(CO)(CN)] [Na 18-crwon-6] (7)	26
2.4.10合成[P(Bu)3Co(NO)(CO)(CN)] [Na 18crwon-6] (8)	27
2.4.11合成[P(Ph)3Co(NO)(CO)(CN)] [PPh4] (9)	27
2.4.12合成[P(OEt)3Co(NO)(CO)(CN)] [Na] (10)	28
2.4.13合成[(CO)2Co(NO) (CN)] [PPh4] (11)	29
2.4.14合成meso-1,3-Bis[(mercaptoethyl)phenylphosphino]propane	30
2.4.15合成Fe(CO)2(NO)2	31
2.4.17合成(H2meppp)Fe(CO)(NO)2 (a)	31
2.4.16合成(H2meppp)Co(CO)2(NO) (b)	31
2.4.18合成(H2meppp)Fe (NO)2 (c)	32
2.4.19合成(H2meppp)Co(CO)(NO) (d)	32
2.4.22合成(H2meppp)Fe(NO) (e)	33
2.4.21合成N,N’-bis(2-merca-ptoethyl)-1,4-diazacycloheptane (N2S2)	33
2.4.23合成[(NO)Fe(N2S2)Fe(NO)2]BF4 (f)	34
2.5 電化學分析 (循環伏安法)	35
2.5.1電化學分析之條件	35
2.5.2量測方法	35
第三章 結果與討論	36
3.1 鈷錯合物 (L)Co(CO)2(NO) 的合成與紅外線光譜分析	36
3.2 鈷錯合物 [(L)Co(CO)(NO)(CN)]- 的合成與紅外線光譜分析	43
3.2 X光單晶繞射分析	51
3.3 雙磷雙硫配位基的鐵/鈷金屬化合物的合成與紅外線光譜分析	58
3.4 亞硝基鐵錯合物與氧化石墨烯產氫測試	68
第四章 結論	75
參考文獻	77

 
圖表目錄:
圖1-1: Tolman electronic parameter	4
圖1-2: 單牙配位基	5
圖1-3: (a).[FeFe] Hydrogenase , (b).[NiFe] Hydrogenase , (c).[Fe]-Hydrogenase	8
圖1-4:(a) 雙鐵氫化酶活性中心, (b) 亞硝基鐵錯合物	9
圖1-5: (a). 鐵鎳氫化酶活性中心, (b). 雙磷雙硫氫化酶模型	10
圖1-6: Enemark-Feltham的計算法	12
圖1-7: 雙原子配位鈷錯合物	13
圖1-8: (a) 雙氮雙硫亞硝基鐵錯合物 (b) 雙磷雙硫鐵錯合物	14
圖1-9: 氧化石墨烯	15



圖3-1: 六種單取代鈷錯合物合成示意圖	37
圖3-2: 化合物(1)	38
圖3-3: 化合物(2)	38
圖3-4: 化合物(3)	39
圖3- 5: 化合物(4)	39
圖3-6: 化合物(5)	40
圖3-7: 化合物(6)	40
圖3-8: [(L)Co(CO)(NO)(CN)]- 化合物的合成	43
圖3-9: 化合物7	44
圖3-10: 化合物8	45
圖3-11: 化合物9	45
圖3-12: 化合物10	46
圖3-13: 化合物11	47
圖3-14: Ni(PR3)(CO)3 的vCO 對鈷錯合物 vCO vNO vCN波數作圖	49
圖3-15: 化合物 [P(Cy)3Co(NO)(CO)(CN)] [Na 18crwon-6] (7) 單晶結構及其鍵長[Å]與鍵角[°]:	52
圖3-16: 化合物 [P(Ph)3Co(NO)(CO)(CN)] [PPh4] (9) 單晶結構及其鍵長[Å]與鍵角[°]:	53
圖3-17: 化合物 [(CO)2Co(NO)(CN)] [PPh4] (11) 單晶結構及其鍵長[Å]與鍵角[°]:	54
圖3-18: Fe(CO)2(NO)2 VS化合物a	59
圖3-19: 推測化合物a可能之結構	60
圖3-20: Co(CO)3(NO) vs化合物b	61
圖3-21: 推測化合物(b)可能之結構	61
圖3-22: 化合物a vs化合物c	62
圖3-23: 推測化合物c 可能之結構	63
圖3-24: 化合物b vs 化合物d	64
圖3-25: 推測化合物d 可能之結構	64
圖3-26: 亞硝基混合物	66
圖3- 27: 化合物(e)	66
圖3-28: (a)文獻中(N2S2)Fe(NO)之結構 (b)推測化合物(e)的結構	67
圖3-29: 化合物f 結構 {Fe(NO)}7–{Fe(NO)2}9	68
圖3-30: 化合物f 測試氧化還原電位	69
圖3-31: 在金表面工作電極上吸附 GO後測試酸催化反應	71
圖3-32: 在 DCM 中測試待測物並滴加 GO 測試氧化還原電位	72
圖3-33: 在 DCM 系統加入 GO 測試酸催化性	73

表1-1: trans-RhL2(CO)X 各式配位基錯合物的 CO 振動頻率	7
表1-2: ㄧ氧化氮的特性及其性質	11

表3-1: L (CO)2Co(NO) 在 THF 溶液中 FT-IR峰值	41
表3-2: [(L)Co(CO)(NO)(CN)]-	47
表3-3: 結構的探討化合物 (7) (9) (11) 鍵長與鍵角	55

 
附錄
S-1: (NHC-Me)(CO)2Co(NO) (1) 溶在 THF 的紅外線光譜圖	80
S-2: (NHC-iMes)(CO)2Co(NO) (2) 溶於THF的紅外線光譜圖	80
S-3: P(Cy)3(CO)2Co(NO) (3) 溶於THF的紅外線光譜圖	81
S-4: P(Bu)3(CO)2Co(NO) (4) 溶於THF的紅外線光譜圖	81
S-5: [P(Ph)3Co(NO)(CO)(CN)] [PPh4] (9) 溶於THF的紅外線光譜圖	82
S-6: P(OEt)3(CO)2Co(NO) (6) 溶於THF的紅外線光譜圖	82
S-7: [P(Cy)3Co(NO)(CO)(CN)] [Na 18-crwon-6] (7) 溶於THF的紅外線光譜圖	83
S-8: [P(Bu)3Co(NO)(CO)(CN)] [Na 18crwon-6] (8) 溶於THF的紅外線光譜圖	83
S-9: [P(Ph)3Co(NO)(CO)(CN)] [PPh4] (9) 溶於THF的紅外線光譜圖	84
S-10: [P(OEt)3Co(NO)(CO)(CN)] [Na] (10) 溶於THF的紅外線光譜圖	84
S-11: [(CO)2Co(NO) (CN)] [PPh4] (11) 溶於THF的紅外線光譜圖	85
S-12: (H2meppp)Fe(CO)(NO)2 (a) 溶於THF的紅外線光譜圖	85
S-13: (H2meppp)Co(CO)2(NO) (b) 溶於THF的紅外線光譜圖	86
S-14: (H2meppp)Fe (NO)2 (c) 溶於THF的紅外線光譜圖	86
S-15: (H2meppp)Co(CO)(NO) (d) 溶於THF的紅外線光譜圖	87
S-16: (H2meppp)Fe(NO) (e) 溶於MeCN的紅外線光譜圖	87
S-17: meso-1,3-Bis[(mercaptoethyl)phenylphosphino]propane	88

Table S-18: [P(Cy)3Co(NO)(CO)(CN)] [Na 18-crwon-6] (7)晶體結構	89
Table S-19: [P(Ph)3Co(NO)(CO)(CN)] [PPh4] (9)晶體結構	93
Table S-20: [Co(NO)(CO)2(CN)] [PPh4] (11) 晶體結構	97

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