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研究生：	陳咨佐 Chen, Tzu-Tso
論文名稱：	釩硫化合物配位基上的反應活性之探討 The Ligand-based Reactivity of Vanadium-thiolate Complexes
指導教授：	許鏵芬 Hsu, Hua-Fen
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2010
畢業學年度：	98
語文別：	英文
論文頁數：	104
中文關鍵詞：	釩、釩硫化合物、金屬硫錯合物、二氯甲烷、硝酸
外文關鍵詞：	vanadium-thiolate complexes, vanadium, metal-thiolate complexes, ligand-based, dichloromethane, HNO3, vanadium-nitrosyl complex, oxygenation
相關次數：	點閱：90 下載：2
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在這份研究中，我們發現了五種釩硫錯合物並鑑定其性質。金屬硫錯合物的反應性已經在文獻上廣為探討，但是對於前過渡金屬的金屬硫錯合物，這一方面的課題還有待深入研究。在此，我們合成出一釩三價錯合物：[VIII(PS2」SH)2][PPh4] (1)。此化合物1可以對二氯甲烷進行親核反應而形成化合物 [VIII(PS3」)Cl][PPh4] (2) 及 [VIV((PS3」)2CH2)] (3)。在沒有二氯甲烷的環境下，化合物1 可以和空氣中的氧氣反應，這些反應包括金屬中心的氧化、雙硫鍵的形成以及硫配位基上的氧原子加成，形成了化合物 [VIV(PS2」SH)(PS3」)][PPh4] (4a) 、 [VIII(P2S4」)(S-S)-][PPh4] (5) 以及其他的釩氧硫化合物 (vanadium sulfenate/disulfenate complexes)，這些釩硫化合物的反應性可以用光譜儀及質譜儀來檢視。化合物1, 2 , 3, 4a 亦經由X-ray單晶繞射來鑑定其結構。除此之外，我們也合成了一種用一氧化氮做為配位基的釩金屬錯合物：[V(PS3」)NO][PPh4] (6)。但是對於化合物6的合成路徑至今還不清楚，推測可能是經由被汙染的硝酸而來。對於上述的反應，我們期待更進一步的研究。

At this work, five vanadium-thiolate complexes have been found and characterized. The reactivity of metal-thiolate complexes has been investigated extensively in literatures. In contrast, such chemistry has not been well explored for early-transition metal-thiolate complexes. Herein, we obtain a vanadium (III) complex, [VIII(PS2」SH)2][PPh4] (1), that can undergo nucleophilic attack toward to dichloromethane and form [VIII(PS3」)Cl][PPh4] (2) and [VIV((PS3」)2CH2)] (3). With the absence of CH2Cl2, complex 1 exhibited several types reactivity toward to dioxygen. They include metal-center oxidation, disulfide formation, and oxygenase on metal bound thiolate, leading to the formation of [VIV(PS2」SH)(PS3」)][PPh4] (4a), [VIII(P2S4」)(S-S)-][PPh4] (5) and vanadium sulfenate/disulfenate complexes, respectively. These resulting products have been identified by spectroscopies and mass spectrometry. In particular, complexes 1, 2, 3, 4a have been structurally characterized by X-ray crystallography. In addition, a {V-NO}4 compound, [V(PS3」)NO][PPh4] (6), was also isolated and characterized. The formation of this vanadium-nitrosyl species is not clear, likely from contaminated nitric acid in the reaction. Further investigation is necessary to have a better understanding of this chemistry.

Table of Contents
Abstract……………………………………………………………………………………..I
Abstract in Chinese……………………………………………………………………….II
Table of Contents…………………………………………………………………………III
List of Figures…………………………………………….……………………………….V
List of Tables………………………………………………………………….…………VIII
List of Schemes…………………………………………………………………….…  IX
Abbreviations……………………………………………………………………………..XI
Chapter 1: Introduction…………………………………………………..1
1.1. Vanadium-thiolate Chemistry………………………………………………….2
1.2. Reactivity of Metal-thiolate Complexes….…………………………………...7
1.3. Biochemistry of Nitric Oxide………………………………………………….12
Chapter 2: Experimental section………………………………………15
Chapter 3: Results…………………………………………………….…21
3.1. Synthesis……………………………………………..………………………..22
3.2. X-ray Structural Determination……………..…………………………...…27
3.3. Nuclear Magnetic Resonance Spectra of Vanadium Complexes………..44
3.4. Comparison of Ultraviolate-visible Spectra…………………………………47
3.5. MASS Spectrometry Analysis……………………………………………..…51
3.6. Electrochemical Results……………………………………...………………57
Chapter 4: Discussions………………………………………………....61
4.1. Ligand-based Nucleophilic Attack Toward to Dichloromethane………….62
4.2. Metal-center Oxidation, S-based Oxygenation and The 
Formation of Disulfide towards to Dioxygen………………………………..69
Chapter 5: Conclusions…………………………………..…………….78
References…………………………………………….……………..……83
Appendix A………………………………………………………………..87
Appendix B………………………………………………………………..94
















List of Figures
Chapter 1
Figure 1-1. The mechanism of VHPOs transferring thiolether to sulfoxide…………3
Figure 1-2. The active site of chloroperoxidase (VClPO)……………………………..3
Figure 1-3. The active site of vanadium nitrogenases.………………….…………….4
Figure 1-4. Vanadate serves as insulin mimic to inhibit PTP…..……………………..6
Figure 1-5. The nonoxovandium complex: Amavidin………………………………….6
Figure 1-6. Disulfide bond cleavage and formation reaction occurred on the 
ruthenium and nickel complexes…………………………………………...8 
Figure 1-7. Oxygenation occurred on the ruthenium-thiolate complexes.…...……...8
Figure 1-8. Nickel-thiolate complexes showed nucleophilic attack ability.…….…….9
Figure 1-9. Dichloromethane was activated by ruthenium complex…………………9
Figure 1-10. Dimeric molybdenum complexes activate dibromomethane to form the 
methylene-bridge…………………………………………………………10
Figure 1-11. L-arginine turn to L-citrulline and nitric oxide through nitric oxide 
synthase enzymes………………………………………………………..12
Figure 1-12. Mechanism of DNICs complex transferring NO2 to NO………………13
Chapter 3
Figure 3-1. X-ray structure of [VIII(PS2」SH)2][PPh4] (1)…………………..…..……..28
Figure 3-2. X-ray structure of [VIV((PS3」)2CH2)] (3)….………………………………32
Figure 3-3. Thermal ellipsoid plots of metal center of complex 3, [VIV(PS3」)2CH2] 
           ………………………………………………………………………………34
Figure 3-4. X-ray structure of [VIV(PS2」SH)(PS3」)][AsPh4] (4b)…………..………..36
Figure 3-5. Thermal ellipsoid plots of metal center of complex 4b,
 [VIV(PS2」SH)(PS3」)][AsPh4] (4b)…………..…………………………….36
Figure 3-6. X-ray structure of [V(PS3」)NO][PPh4] (6)……………………..………..41
Figure 3-7. Thermal ellipsoid plots of metal center of complex 6, 
[V(PS3」)NO][PPh4] (6)………………………..………………………….43
Figure 3-8. 400MHz 1H-NMR spectrum of [VIII(PS2」SH)2][PPh4] (1).….……….….44
Figure 3-9. 400MHz 1H-NMR spectrum of [VIII(PS3」)Cl][PPh4] (2)….……………...45
Figure 3-10. 400MHz 1H-NMR spectrum of [VIV((PS3」)2CH2)] (3)….….…………45
Figure 3-11. 400MHz 1H-NMR spectrum of [VIV(PS2」SH)(PS3」)][PPh4] (4a)……..46
Figure 3-12. Uv/vis spectrum of [VIII(PS2」SH)2][PPh4] (1)….……………..….…..…48
Figure 3-13. Uv/vis spectrum of [VIII(PS3」)Cl][PPh4] (2)….……………….…………48
Figure 3-14. Uv/vis spectrum of [VIV((PS3」)2CH2)] (3)….……………………..…...49
Figure 3-15. Uv/vis spectrum of [VIV(PS2」SH)(PS3」)][PPh4] (4a).………………….49
Figure 3-16. Uv/vis spectrum of [V(PS3」)NO][PPh4] (6)……………………………..50
Figure 3-17. FAB-MASS spectrum of [VIII(PS2」SH)2][PPh4] (1)…….….…………...51
Figure 3-18. ESI-MASS spectrum of [VIII(PS2」SH)2][PPh4] (1)….…….………..…..52
Figure 3-19. FAB-MASS spectrum of [VIV((PS3」)2CH2)] (3)…..……………….…..53
Figure 3-20. ESI-MASS spectrum of [VIV((PS3」)2CH2)] (3)………………….………54
Figure 3-21. ESI-MASS spectrum of [VIV(PS2」SH)(PS3」)][PPh4] (4a)…………….55
Figure 3-22. ESI-MASS spectrum of [V(PS3」)NO][PPh4] (6)……………………….56
Figure 3-23. Cyclic voltammogram of [VIII(PS2」SH)2][PPh4] (1)………….……..….57
Figure 3-24. Cyclic voltammogram of [VIII(PS3」)Cl][PPh4] (2)…….………………...58
Figure 3-25. Cyclic voltammogram of [VIV((PS3」)2CH2)] (3)..…….……………….59
Figure 3-26. Cyclic voltammogram of [VIV(PS2」SH)(PS3」)][PPh4] (4a)……………60
Chapter 4
Figure 4-1. 300 MHz 1H-NMR Spectra of PS3」H3 and residual solution after
 complex 1 changed to complex 2…………………………….........…….63
Figure 4-2. Variation UV/vis spectra of [VIII(PS2」SH)2][PPh4] (1) in CH2Cl2……….64
Figure 4-3. The 500 MHz 1H-NMR spectra of [VIII(PS2」SH)2][PPh4] (1), complex (1) 
transferring to (2), and [VIII(PS3」)Cl][PPh4] (2) in CD2Cl2……………....65
Figure 4-4. ESI-MASS spectra of [VIV((PS3」)2CH2)] (3) and deuterated complex 3.
          ……………………………………………………………………………….68
Figure 4-5. ESI-MASS spectrum of [VIII(PS2」SH)2][PPh4] (1) in the range of 
1190m/z to 1250 m/z……………………………………………………….69
Figure 4-6. The MS/MS spectrum of [VIII(P2S4」)(S-S)]- (5) (1193 m/z)……………71
Figure 4-7. The MS/MS spectrum of [VIV(PS2」SH)(PS3」)][PPh4] (4a) (1194 m/z) 
………………………………………………………………………...……..73
Figure 4-8. Variation UV/vis spectra of 1 in CH3CN in the air……………………….75
Figure 4-9. ESI-MASS spectrum of [VIV((PS3」)2CH2)] (3) in the range of 1190m/z to 
1320 m/z…………………………………………………………………….76
Figure 4-10. ESI-MASS spectrum of [VIV(PS2」SH)(PS3」)][PPh4] (4a) in the range of 
1190m/z to 1250 m/z……………………………………………….…….77
Chapter 5
Figure 5-1. Reaction occurred in generating thiyl radicals, or by reaction with 
electrophiles, or oxygen…………………………………………………...82





List of Tables
Chapter 3
Table 3-1. X-ray structure parameters of [VIII(PS2」SH)2][PPh4] (1)………..……….29
Table 3-2. Selected bond lengths and angles of [VIII(PS2」SH)2][PPh4] (1)………...30
Table 3-3. Comparison of V-S average bond length comparison of six-coordinated 
V(III) complexes……………………….………….…………………………30
Table 3-4. X-ray structure parameters of [VIV((PS3」)2CH2)] (3)……………………33
Table 3-5. Selected bond lengths and angles of [VIV((PS3」)2CH2)] (3)……….........34
Table 3-6. X-ray structure parameters of [VIV(PS2」SH)(PS3」)][PPh4] (4a)……...…37 
Table 3-7. Selected bond lengths and angles of [VIV(PS2」SH)(PS3」)][PPh4] (4a)..38
Table 3-8. Comparison of bond lengths for selected vanadium-thiolate complexes.
         …………………………………………………………………………………40
Table 3-9. X-ray structure parameters of [V(PS3」)NO][PPh4] (6)………………......42
Table 3-10. Selected bond lengths and angles of [V(PS3」)NO][PPh4] (6)…………43
Table 3-11. Extinction coefficient and absorption wavelength of complex 1 to 4a
……………………………………………………………………………….47
Table 3-12. Cyclic valtommetry studied of complex 1 to 4a…………………………60







List of Schemes
Chapter 1
Scheme 1-1. Reaction of Vanadate-dependent Haloperoxidases (VHPOs)………..3
Scheme 1-2. The reaction of nitrogenases in biosystems…………………………….4
Scheme 1-3. Disulfide bond formation and cleavage through vanadium complexes
            ………………………………………………………………………………6
Chapter 3
Scheme 3-1. The synthetic route of [VIII(PS2」SH)2][PPh4] (1)…………………..….23
Scheme 3-2. The synthetic route of [VIII(PS3」)Cl][PPh4] (2)……………………...…23
Scheme 3-3. The synthetic route of [VIV((PS3」)2CH2)] (3)…………………….…….24
Scheme 3-4. The synthetic route of [VIV(PS2」SH)(PS3」)][PPh4] (4a).….………….25
Scheme 3-5. The synthetic route of [V(PS3」)NO][PPh4] (6)………………………...26
Scheme 3-6. Six-coordinated vanadium(III) complexes with multi-thiolate ligands
            …………………………………………………………………………….31
Scheme 3-7. Selected vanadium (III) and (IV) thiolate complexes in different
 coordination number…………………………………………………….39
Chapter 4
Scheme 4-1. The conversion of [VIII(PS2」SH)2][PPh4] (1) to [VIII(PS3」)Cl][PPh4] (2)
 in CH2Cl2………………………………………………………………….63
Scheme 4-2. The relationship of [VIII(PS2」SH)2][PPh4] (1) and [VIII(PS3」)Cl][PPh4] 
(2)………………...……………………………………………………….66
Scheme 4-3. Isotopic experiment in the synthesis of [VIV((PS3」)2CH2)] (3) and 
deuterated 3, [VIV((PS3」)2CD2)]................…………………………….67
Scheme 4-4. S-based oxygenation of [VIII(PS2』SH)2][PPh4] (1)…………………….70

Scheme 4-5. Molecule conformations corresponding to the ion peak of the MS/MS
            spectrum of 1193 m/z………….………………………………………..72
Scheme 4-6. Molecule conformations corresponding to the ion peak of the MS/MS
            spectrum of 1194 m/z……………………………………………………74
Scheme 4-7. S-based oxygenation of [VIV((PS3」)2CH2)] (3)………………………76
Chapter 5
Scheme 5-1. The overall chemical reactions of complexes 1 to 6………………….79
Scheme 5-2. The synthetic routes of two vanadium (IV) complexes……………….81


                                    

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