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研究生：	林稚展 Lin, Chih-Jan
論文名稱：	鉛配位化學的研究 Coordination chemistry of lead(II) 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：	2013
畢業學年度：	101
語文別：	英文
論文頁數：	108
中文關鍵詞：	鉛硫錯合物、核磁共振光譜
外文關鍵詞：	lead(II), thiolate, Nucleic Magnetic Resonance Spectroscopy
相關次數：	點閱：65 下載：2
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鉛一直以來對於人類與環境都是一種有毒的金屬,在自然界中植物可以產生多硫的解毒劑用來移去鉛,相反的鉛也會與人體中含硫的生物配位基反應而呈現toxic effect。為了要去了解鉛毒性的基礎化學,所以非常需要完整鉛配位化學的光譜。在本論文中,我們使用了一系列的磷硫配位基PS3, PS3’ and PS3” PhPS2’’ and tBuPS2” PhPS1”合成出六個鉛硫錯合物來探討其化學,分別是[N(CH3)3(PhCH2)][Pb(PS3)] (1), [N(C7H15)4] [Pb(PS3’)] (2), [N(C2H5)4][Pb(PS3”)] (3a and 3b), [Pb(PhPS2”)] (4), [Pb(PhPS1”)2] (5),and [Pb(tBuPS2”)] (6),這些錯合物的合成與X-ray結構的鑑定在我們實驗室裡早已建立,為了要去更加了解這些錯合物的配位化學,所以我們使用了一些物理方法來鑑定例如核磁共振光譜、X-ray繞射、X-ray吸收儀器並且探討這些錯合物的固態和液態的配位化學。

Lead(II) ion has been known to a toxic element for human being and environment. In nature, plants can produce antidotes which contain sulfur ligands to remove lead ion. In contrast, lead(II) ion shows the toxic effect by interacting with sulfur containing bioligands in human body. To provide insights for understanding the fundamental chemistry of the lead(II) toxicity, it is very essential to have a full scope of the lead(II) coordination chemistry. At this particular work, we investigate lead(II) sulfur chemistry by utilizing a series of thiolatophosphine ligands, such as tris(benzenethiolato)phosphine (PS3, PS3’ and PS3”), bis(benzenethiolato)phosphine(PhPS2’’ and tBuPS2”), and benzenethiolatophosphine (PhPS1”). We isolated six lead complexes with these ligands. They are [N(CH3)3(PhCH2)][Pb(PS3)] (1), [N(C7H15)4] [Pb(PS3’)] (2), [N(C2H5)4][Pb(PS3”)] (3a and 3b), [Pb(PhPS2”)] (4), [Pb(PhPS1”)2] (5),and [Pb(tBuPS2”)] (6). The synthesis and X-ray structures have been established previously in our laboratory. To study the coordination chemistry of these complexes in depth, several physical methods such as NMR (1H, 31P, and 207Pb), X-ray absorption spectroscopy in both solid and solution states, were applied on these complexes.

Abstract	I
中文摘要	II
誌謝	III
Abbreviations of the ligands	IV
List of Table	VII
List of Figure	VIII
List of Scheme	XI
Chapter 1 Introduction
1.1 General Introduction	1
1.2 The effect of lead in organism	1
1.3 Stereochemistry of Pb-complexes: Holo-directed and Hemi-directed coordination	5
1.4 Lead(II) thiolate complexes and their 207Pb NMR in literature	6
1.5 Motivation	9
Chapter 2 Experiments
2.1 Materials	11
2.2 Syntheses	12
Synthesis of [N(CH3)3(CH2Ph)][Pb(PS3)](1)	12
Synthesis of [N(C7H15)4][Pb(PS3’)](2)	12
Synthesis of [N(C2H5)4][Pb(PS3”)](3a)(3b)	13
Synthesis of [Pb(PhPS2”)](4)	13
Synthesis of [Pb(PhPS1”)2](5)	13
Synthesis of [Pb(tBuPS2”)](6)	14
X-ray Crystallographic Data Collection	14
Elemental Analysis	14
Nucleic Magnetic Resonance Spectroscopy	14
Mass Spectrometry	15
XAS Data Collection	15
Chapter 3 Results and discussion
Synthesis and Characterization of [N(CH3)3(CH2Ph)][Pb(PS3)](1)	16
X-ray Structure	16
Electrospray ionization Mass Spectrum	19
Nuclear Magnetic Resonance Spectroscopic Studies	21
(A)207Pb solid NMR	21
(B) 31P{207Pb J-HMQC 2D solid NMR	21
(C) 207Pb solution-state NMR	23
(D) The comparison of solid-state and solution-state NMR	23
L-edge X-ray absorption spectroscopic studies	24
Synthesis and Characterization of [N(C7H15)4][Pb(PS3’)](2)	26
X-ray Structure	26
Electrospray ionization Mass Spectrum	29
Nucleic Magnetic Resonance Spectroscopy characterization	30
(A)207Pb and solid NMR	30
(B)31P{207Pb} J-HMQC 2D solid NMR	31
(C) 207Pb and 31p solution-state NMR	32
(D) The comparison of solid-state and solution-state NMR	33
Powder X-ray diffraction	34
L-edge X-ray absorption spectroscopic studies	35
Synthesis and Characterization of [N(C2H5)4][Pb(PS3”)](3a)(3b)	37
X-ray Structure	37
Electrospray ionization Mass Spectrum	42
Nucleic Magnetic Resonance Spectroscopy characterization	44
(A) 207Pb and 31P solid NMR	44
(B) 207Pb and 31P solution NMR	44
L-edge X-ray absorption spectroscopic studies	45
Synthesis and Characterization of [Pb(PhPS2”)](4)	47
X-ray Structure	47
Electrospray ionization Mass Spectrum	50
Nuclear Magnetic Resonance Spectroscopic Studies	52
(A)207Pb solid NMR	52
(B)31P{207Pb} J-HMQC 2D solid NMR	52
(C) 207Pb solution NMR	53
(D)The difference of solid and solution NMR	54
L-edge X-ray absorption spectroscopic studies	55
Synthesis and Characterization of [Pb(PhPS1”)2](5)	57
X-ray Structure	57
Electrospray ionization Mass Spectrum	60
Nuclear Magnetic Resonance Spectroscopic Studies	62
(A)207Pb solid NMR	62
(B) 31P{207Pb} J-HMQC 2D solid NMR	62
(C) 207Pb solution NMR	63
(D) The comparison of solid-state and solution-state NMR	64
L-edge X-ray absorption spectroscopic studies	65
Synthesis and Characterization of [Pb(tBuPS2”)](6)	67
X-ray Structure	67
Electrospray ionization Mass Spectrum	70
Nuclear Magnetic Resonance Spectroscopic Studies	71
L-edge X-ray absorption spectroscopic studies	71
Conclusion	73
Reference	75
Appendix A	77
Appendix B	96
Appendix C	102


List of Table
Chapter 1 Introduction
Table 1-1. Chemical shift of 207Pb NMR for Pb complexes …….……….................7
Chapter 3 Results and discussion
Table 2-1. Selected bond lengths (Å) for complex 1................................................17
Table 2-2. Selected bond angles (deg) for complex 1……………………....……...17
Table 2-3. Selected bond lengths (Å) for complex 2................................................27
Table 2-4. Selected bond angles (deg) for complex 2...............................................27
Table 2-5. Selected bond lengths (Å) for complex 3a..............................................38
Table 2-6. Selected bond angles (deg) for complex 3a.............................................38
Table 2-7. Selected bond lengths (Å) for complex 3b..............................................41
Table 2-8. Selected bond angles (deg) for complex 3b……………………….........41
Table 2-9. Selected bond lengths (Å) for complex 4................................................48
Table 2-10. Selected bond angles (deg) for complex 4.............................................48
Table 2-11. Selected bond lengths (Å) for complex 5..............................................58
Table 2-12. Selected bond angles (deg) for complex 5.............................................58
Table 2-13. Selected bond lengths (Å) for complex 6..............................................68
Table 2-14. Selected bond angles (deg) for complex 6.............................................68
Table 3-1. Summaries of the coordinations, bond lengths and chemical shifts of Pb complexes..................................................................................................................74
Table 4-1. CIF check of [N(CH3)3(CH2Ph)][Pb(PS3)](1)……………………….....77
Table 4-2. CIF check of [N(C7H15)4][Pb(PS3’)](2)..................................................80
Table 4-3. CIF check of [N(C2H5)4][Pb(PS3”)](3b).................................................83
Table 4-4. CIF check of [Pb(PhPS2”)](4)..................................................................88
Table 4-5. CIF check of [Pb(PhPS1”)2](5).................................................................91
Table 3-6. CIF check of [Pb(tBuPS2”)](6).................................................................94

List of Figure
Chapter 1 Introduction
Figure 1-1. Glutathione (γ-L-glutamyl-L-cysteinylglycine, GSH, denoted AH3 in it’s triprotonated form)	2
Figure 1-2. Thiol containing side chain of  amino-acid: Cysteine	3
Figure 1-3. Proposed structure for lead(II) Glutathione complexe,  Pb(GSH)3	3
Figure 1-4. Ribbon diagram of the fold of the ALAD monomer(left) Formation of E. coli ALAD dimers (right).10	4
Figure 1-5. Organization of the E. coli ALAD octamer.10	4
Figure 1-6. Lead(II) thiolate complexes in literature	8
Figure 1-7. Thiolatophosphineligands used in this research	10
Figure 1-8. Lead-thiolate complex 1~6	10
Chapter 2 Results and discussion
[N(CH3)3(PhCH2)][Pb(PS3)] (1)
Figure 2-1. ORTEP diagram of complex 1 shown with 35% thermal ellipsoids. H atoms and cations are omitted for clarity.	18
Figure 2-2. Intermolecular interaction of complex 1 viewed alone c with axis	18
Figure 2-3.Packing diagram along with b axis in complex 1	19
Figure 2-4.Negative-Mode ESI-MS spectrum of complex 1 measured in CH2Cl2	20
Figure 2-5. Isotope pattern of complex 1	20
Figure 2-6. 207Pb Solid-state NMR spectrum of complex 1	21
Figure 2-7. 31P Solid-state NMR spectrum of complex 1	22
Figure 2-8. Solid 2D NMR for 31P and 207Pb of complex 1	22
Figure 2-9. Solution 207Pb NMR spectra of complex 1 in CD2Cl2	23
Figure 2-10. The comparison of (A) solid-state and (B) solution-state 207Pb NMR of complex 1	24
Figure 2-11. Pb LIII-edge XANES spectra of complex 1 in solid- and solution-state	25
Figure 2-12. Pb LIII-edge EXAFS spectra of complex 1 in solid- and solution-state	25
[N(C7H15)4] [Pb(PS3’)] (2)
Figure 2-13. ORTEP diagram of complex 2 shown with 35% thermal ellipsoids. H atoms and cations are omitted for clarity	27
Figure 2-14. No intermolecular interaction of complex 2 viewed alone with c axis	28
Figure 2-15.Packing diagram along with b axis in complex 2	28
Figure 2-16.Negative-Mode ESI-MS spectrum of complex 2 measured in CH2Cl2	29
Figure 2-17. Isotope pattern of complex 2 (A) experimental pattern and (B) theoretic pattern.	30
Figure 2-18. 207Pb Solid-state NMR spectrum of complex 2	31
Figure 2-19. 31P Solid-state NMR spectrum of complex 2	31
Figure 2-20. Solid 2D NMR for 31P and 207Pb of complex 2	32
Figure 2-21. Solution 31P NMR spectra of complex 2 in d-DMSO………………..33
Figure 2-22. Solution 207Pb NMR spectra of complex 2 in CD2Cl2	33
Figure 2-23. The comparison of (A) solid-state and (B) solution-state 207Pb NMR of complex 2	34
Figure 2-24. Powder XRD pattern of complex 2 (A) theoretic pattern and (B) experimental pattern.	35
Figure 2-25. Pb LIII-edge XANES spectra of complex 2 in solid- and solution-state…………………………………………………………………….... 36 
Figure 2-26. Pb LIII-edge EXAFS spectra of complex 2 in solid- and solution-state……………………………………………………………………… 36    
[N(C2H5)4][Pb(PS3”)] (3a and 3b)
Figure 2-27. ORTEP diagram of complex 3a shown with 35% thermal ellipsoids. H atoms and cations are omitted for clarity.	39
Figure 2-28. Intermolecular interaction of complex 3a viewed alone c with axis	39
Figure 2-29. Packing diagram along with a axis in complex 3a	40
Figure.2-30. ORTEP diagram of complex 3b shown with 35% thermal ellipsoids. H atoms and cations are omitted for clarity	41
Figure 2-31. Packing diagram along with b axis in complex 3b	42
Figure 2-32. Negative-Mode ESI-MS spectrum of complex 3 measured in CH2Cl	.43
Figure 2-33. Isotope pattern of complex 3 (A) experimental pattern and (B) theoretic pattern.	43
Figure 2-34. 31P Solid-state NMR spectrum of complex 3	44
Figure 2-35. 207Pb Solution-state NMR spectrum of complex 3…………………...45
Figure 2-36. 31P Solution-state NMR spectrum of complex 3	45
Figure 2-37. Pb LIII-edge XANES spectra of complex 3 in solid- and solution-state	46
Figure 2-38. Pb LIII-edge EXAFS spectra of complex 3 in solid- and solution-state ……....................................................................................................46  
[Pb(PhPS2”)] (4)
Figure 2-39. ORTEP diagram of complex 4 shown with 35% thermal ellipsoids. H atoms are omitted for clarity	48
Figure 2-40. Intermolecular interactions of complex 4 viewed alone a with axis	49
Figure 2-41. Packing diagram along with c axis in complex 4	49
Figure 2-42. Positive-Mode ESI-MS spectrum of complex 2 measured in CH2Cl2	50
Figure 2-43. Isotope pattern of complex 4 (A) experimental pattern and (B) theoretic pattern.	51
Figure 2-44. Isotope pattern of complex 4 (A) experimental pattern and (B) theoretic pattern.	51
Figure 2-45. 207Pb Solid-state NMR spectrum of complex 4	52
Figure 2-46. 31P Solid-state NMR spectrum of complex 4	53
Figure 2-47. Solid 2D NMR for 31P and 207Pb of complex 4	53
Figure 2-48. Solution 207Pb NMR spectra of complex 4 in CD2Cl2	54
Figure 2-49. The comparison of (A) solid-state and (B) solution-state 207Pb NMR of complex 4	55
Figure 2-50. Pb LIII-edge XANES spectra of complex 4 in solid- and solution-state	56
Figure 2-51. Pb LIII-edge EXAFS spectra of complex 4 in solid- and solution-state	56
[Pb(PhPS1”)2](5)
Figure.2-52. ORTEP diagram of complex 5 shown with 35% thermal ellipsoids. H atoms and are omitted for clarity	58
Figure 2-53. Intermolecular interactions of complex 5 viewed alone b with axis	59
Figure 2-54. Packing diagram along with b axis in complex 5	59
Figure 2-55.Negative-Mode ESI-MS spectrum of complex 5 measured in CH2Cl2.	60
Figure 2-56. Isotope pattern of complex 5 (A) experimental pattern and (B) theoretic pattern.	61
Figure 2-57. Isotope pattern of complex 5 (A) experimental pattern and (B) theoretic pattern.	61
Figure 2-58. 207Pb Solid-state NMR spectrum of complex 5	62
Figure 2-59. 31P Solid-state NMR spectrum of complex 5	63
Figure 2-60. Solid 2D NMR for 31P and 207Pb of complex 5	63
Figure 2-61. Solution 207Pb NMR spectra of complex 5 in CD2Cl2	64
Figure 2-62. The comparison of (A) solid-state and (B) solution-state 207Pb NMR of complex 5	65
Figure 2-63. Pb LIII-edge XANES spectra of complex 5 in solid- and solution-state	66
Figure 2-64. Pb LIII-edge EXAFS spectra of complex 5 in solid- and solution-state	66
[Pb(tBuPS2”)] (6)
Figure 2-65. ORTEP diagram of complex 6 shown with 35% thermal ellipsoids. H atoms are omitted for clarity.	68
Figure 2-66. Intermolecular interactions of complex 6 viewed alone b with axis	69
Figure 2-67. Packing diagram along with b axis in complex 6Figure 1.3 ORTEP diagram of complex 6 shown with 35% thermal ellipsoids. H atoms are omitted for clarity.	69
Figure 2-68.Negative-Mode ESI-MS spectrum of complex 6 measured in CH2Cl2	70
Figure 2-69. Isotope pattern of complex 6 (A) experimental pattern and (B) theoretic pattern..	71
Figure 2-70. Pb LIII-edge XANES spectra at RT of solid and solution for complex 6	72
Figure 2-71. Pb LIII-edge EXAFS spectra of solid and solution for complex 6 at RT	72
Figure 3-1. 1H NMR Spectrum of [N(CH3)3(PhCH2)][Pb(PS3)] (1)........................97
Figure 3-2. 1H NMR Spectrum of [N(C7H15)4] [Pb(PS3’)] (2).................................98
Figure 3-3. 1H NMR Spectrum of [N(C2H5)4][Pb(PS3”)] (3a and 3b).....................99
Figure 3-4. 1H NMR Spectrum of [Pb(PhPS2”)] (4)................................................100
Figure 3-5. 1H NMR Spectrum of [Pb(PhPS1”)2] (5)...............................................101
Figure 3-6. 1H NMR Spectrum of [Pb(tBuPS2”)] (6)...............................................102
Figure 3-7. 31P NMR Spectrum of [N(CH3)3(PhCH2)][Pb(PS3)] (1)......................103
Figure 3-8. 31P NMR Spectrum of [N(C7H15)4] [Pb(PS3’)] (2)...............................104
Figure 3-9. 31P NMR Spectrum of [N(C2H5)4][Pb(PS3”)] (3a and 3b)...................105
Figure 3-10. 31P NMR Spectrum of [Pb(PhPS2”)] (4).............................................106
Figure 3-11. 31P NMR Spectrum of [Pb(PhPS1”)2] (5)............................................107
Figure 3-12. 31P NMR Spectrum of [Pb(tBuPS2”)] (6)............................................108

List of Scheme
Chapter 1 Introduction 
Scheme 1-1. Detoxification mechanisms process…………………………………...2
Scheme 1-2. (A) Holo-directed and (B) Hemi-directed Coordination sphere………5
Scheme 1-3. Lead(II)-ligand interaction in the hemi-directed and holo-directed geometries...................................................................................................................5
Chapter 2 Results and discussion 
Scheme 2-1. Teh reaction scheme of complex 1……………………………….…..16
Scheme 2-2. Teh reaction scheme of complex 2…………………………………...26
Scheme 2-3. Teh reaction scheme of complex 3 ……………………………….….36
Scheme 2-4. Teh reaction scheme of complex 4……………………………….…..46
Scheme 2-5. Teh reaction scheme of complex 5 ……………………………….….56
Scheme 2-6. Teh reaction scheme of complex 6…………………………………...66
                                    

1 Dybowski, C. & Neue, G. Solid state Pb-207 NMR spectroscopy. Prog. Nucl. Magn. Reson. Spectrosc. 41, 153-170, (2002).
2 Briand, G. G., Smith, A. D., Schatte, G., Rossini, A. J. & Schurko, R. W. Probing lead(II) bonding environments in 4-substituted pyridine adducts of (2,6-Me2C6H3S)2Pb: an X-ray structural and solid-state 207Pb NMR study. Inorganic chemistry 46, 8625-8637, (2007).
3 Sharma, P. & Dubey, R. S. Lead toxicity in plants. Brazilian Journal of Plant Physiology 17, 35-52, (2005).
4 Cherian, S. & Oliveira, M. M. Transgenic Plants in Phytoremediation: Recent Advances and New Possibilities. Environmental Science & Technology 39, 9377-9390, (2005).
5 Lasat, M. M. The use of plants for the removal of toxic metals from contaminated soils. (US Environmental Protection Agency, 2000).
6 Mah, V. & Jalilehvand, F. Lead(II) complex formation with glutathione. Inorganic chemistry 51, 6285-6298, (2012).
7 Neupane, K. P. & Pecoraro, V. L. Pb-207 NMR spectroscopy reveals that Pb(II) coordinates with glutathione (GSH) and tris cysteine zinc finger proteins in a PbS3 coordination environment. Journal of inorganic biochemistry 105, 1030-1034, 2011.04.010 (2011).
8 Sneller, F. E. C. et al. Derivatization of Phytochelatins fromSilenevulgaris, Induced upon Exposure to Arsenate and Cadmium: Comparison of Derivatization with Ellman's Reagent and Monobromobimane. Journal of Agricultural and Food Chemistry 48, 4014-4019, (2000).
9 Mishra, S. et al. Lead detoxification by coontail (Ceratophyllum demersum L.) involves induction of phytochelatins and antioxidant system in response to its accumulation. Chemosphere 65, 1027-1039, 2006.03.033 (2006).
10 Erskine, P. T. et al. X-ray structure of 5-aminolevulinic acid dehydratase from Escherichia coli complexed with the inhibitor levulinic acid at 2.0 A resolution. Biochemistry 38, 4266-4276, (1999).
11 Shimoni-Livny, L., Glusker, J. P. & Bock, C. W. Lone Pair Functionality in Divalent Lead Compounds. Inorganic chemistry 37, 1853-1867, (1998).
12 Magyar, J. S. et al. Reexamination of lead(II) coordination preferences in sulfur-rich sites: implications for a critical mechanism of lead poisoning. Journal of the American Chemical Society 127, 9495-9505, (2005).
13 Chen, P. R. et al. Spectroscopic insights into lead(II) coordination by the selective lead(II)-binding protein PbrR691. Journal of the American Chemical Society 129, 12350-12351, (2007).
14 Rekken, B. D., Brown, T. M., Olmstead, M. M., Fettinger, J. C. & Power, P. P. Stable plumbylene dichalcogenolate monomers with large differences in their interligand angles and the synthesis and characterization of a monothiolato Pb(II) bromide and lithium trithiolato plumbate. Inorganic chemistry 52, 3054-3062, (2013).
15 Dean, P. A., Vittal, J. J. & Payne, N. C. Discrete trigonal-pyramidal lead (II) complexes: syntheses and x-ray structure analyses of [(C6H5) 4As][Pb (EC6H5) 3](E= S, Se). Inorganic chemistry 23, 4232-4236 (1984).
16 Yu-chiau, W. Syntheses, Structures, and Characterizations of Lead(II) Complexes in A Sulfur-rich Ligated Environment. (2008).
17 Siegel, R., Nakashima, T. T. & Wasylishen, R. E. Application of Multiple-Pulse Experiments to Characterize Broad NMR Chemical-Shift Powder Patterns from Spin-1/2Nuclei in the Solid State. The Journal of Physical Chemistry B 108, 2218-2226, (2004).

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