成功大學博碩士論文系統

簡易檢索 / 詳目顯示

回結果列表

研究生：	黃啟閔 Huang, Chi-Ming
論文名稱：	四芽磷硫配位基的開發及其雙銅化合物的合成與鑑定 Development of the Tetradentate Diphosphanyl-bisbenzenethiolate S, P, P, S ligand: Synthesis and Characterization of a Dicopper Complex with S, P, P, S ligand
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：	2014
畢業學年度：	102
語文別：	英文
論文頁數：	66
中文關鍵詞：	磷硫配位基、銅硫錯合物
外文關鍵詞：	Thiolatophosphine ligands, copper thiolate complexes
相關次數：	點閱：119 下載：1
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

在生物上有許多金屬蛋白的活化位置是由金屬離子和硫配位環境如半胱氨酸或硫化物所組成。為了瞭解金屬與硫鍵結之間的特性，我們實驗室陸續地開發出了四芽磷硫配位基,P2S2 (H2[P2S2]=1,2-bis(mercaptophenyl- phenyl-phosphino)ethane)以及其衍生物。在此論文中，我們合成以及鑑定P2S2* (H2[P2S2*]=1,2-bis(3-trimethylsilanyl-2mercaptophenyl-phenyl–phosphino) ethane)此四芽磷硫配位基。另外在研究這些四芽磷硫配位基與金屬的反應中，合成出由P2S2’’配位基所形成的雙銅金屬錯合物[Cu2(P2S2’’)(PPh3)2]並且透過X光單晶繞射儀及一些光譜對例如核磁共振光譜，循環伏安法和電噴灑質譜儀對其鑑定。

Many metalloproteins have active sites where metals ions are ligated by biological S-donors such as cysteine and sulfide. To understand the feature of metal sulfur bonds, we have developed a new type of diphosphine-dithiolate ligand, P2S2 (H2[P2S2]=1,2-bis(mercaptophenyl-phenyl-phosphino)ethane) and its derivatives. At this work, the synthesis and characterization of P2S2* (H2[P2S2*] =1,2-bis(3-trimethylsilanyl-2mercaptophenyl-phenyl-phosphino)ethane)is described in detail.
In the continuing efforts to explore the metal chemistry of the tetradentate ligand system, a dicopper(I) complex of P2S2” ligand [Cu2(P2S2’’)(PPh3)2] has been synthesized and characterized by X-ray crystallography, spectroscopies, cyclic voltammetry and ESI-MS.

Abstract	I
中文摘要	II
誌謝	III
List of Contents	IV
List of Schemes	VI
List of Tables	VII
List of Figures	VIII
Abbreviations	XI
Chapter 1. Introduction	1
1-1. Sulfur-rich ligation in metalloproteins	1
1-2. Example of S-only ligand system and related metal complexes	4
1-3. Example of hybrid N/S ligand system and related metal complexes	5
1-4. Example of hybrid P/S ligand system and related metal complexes	6
1-5. Example of copper thiolate complexes	9
1-6. The motivation of this work	13
Chapter 2. Results and Discussion	14
2-1. The overall syntheses description of H2[P2S2’’] and H2[P2S2*] ligand	14
2-1-1. Synthesis of 2-trimethylsilyl-thiophenol	15
Synthesis.	15
2-1-2. Synthesis of O-2(biphenyl)- N,N- dimethylthiocarbamate	16
Synthesis.	16
2-1-3. Synthesis of 2-mercaptobiphenyl	16
Synthesis.	16
2-1-4. Synthesis of [PhPCH2CH2PPh]Li2•(THF)4	17
Synthesis.	17
2-1-5. Synthesis of ClPhPCH2CH2PPhCl	17
Synthesis.	17
2-2. Synthesis and characterization of H2[P2S2’’] and H2[P2S2*] ligand	18
NMR Spectrum of H2[P2S2”] and H2[P2S2*] ligand	19
Electrospray Ionization Mass analysis of H2[P2S2*] ligand	24
IR spectrum of H2[P2S2*] ligand	26
2-3. Synthesis and characterization of [Cu2(P2S2’’)(PPh3)2]	27
Method a.	27
Method b.	27
X-ray structural determination of [Cu2(P2S2’’)(PPh3)2]	28
The chemistry of the synthesis of [Cu2(P2S2’’)(PPh3)2]	34
Powder X-ray diffraction of [Cu2(P2S2’’)(PPh3)2]	34
UV-Vis spectrum of [Cu2(P2S2’’)(PPh3 )2]	35
NMR Spectrum of [Cu2(P2S2’’)(PPh3)2]	36
The electrochemical study of [Cu2(P2S2’’)(PPh3)2]	40
Electrospray Ionization Mass analysis of [Cu2(P2S2’’)(PPh3)2]	43
2-4. On-going metal reactions of H2[P2S2”] ligand	46
Chapter 3. Conclusions	47
Chapter 4. Experiments and Instruments	48
4-1. General procedures	48
X-ray Crystallographic Data Collection and Refinement of the structures	48
Elemental Analysis	48
Nucleic Magnetic Resonance Spectroscopy	48
Infrared Spectroscopy	49
Electrospray Ionization Mass Analysis	49
Uv-Vis Spectroscopy	49
Cyclic Voltammetry	49
4-2. Synthesis	49
[PhPCH2CH2PPh]Li2•(THF)4	49
ClPhPCH2CH2PPhCl	50
2-trimethylsilyl-benzenethiol	50
H2[P2S2’’] ligand	51
Cu(CH3CN)4BF4	51
[Cu2(P2S2’’)(PPh3)2] •2CH2Cl2	51
O-2(biphenyl)-N,N-dimethylthiocarbamate	52
2-mercaptobiphenyl	52
H2[P2S2*] ligand	52
Reference	54
Appendix A	57
Appendix B	63


                                    

1 Hinnemann, B. & Nørskov, J. K. Modeling a Central Ligand in the Nitrogenase FeMo Cofactor. Journal of the American Chemical Society 125, 1466-1467, (2003).
2 Li, S. & Hall, M. B. Modeling the Active Sites of Metalloenzymes. 4. Predictions of the Unready States of [NiFe] Desulfovibrio gigas Hydrogenase from Density Functional Theory. Inorganic Chemistry 40, 18-24, (2000).
3 Rubino, J. T. & Franz, K. J. Coordination chemistry of copper proteins: how nature handles a toxic cargo for essential function. Journal of inorganic biochemistry 107, 129-143, (2012).
4 Belle, C., Rammal, W. & Pierre, J. L. Sulfur ligation in copper enzymes and models. Journal of inorganic biochemistry 99, 1929-1936, (2005).
5 Sellmann, D., Funfgelder, S., Pohlmann, G., Knoch, F. & Moll, M. Transition-metal complexes with sulfur ligands. 55. Nickel complexes with thiolato-thioether ligands including nitrogen and oxygen donors in S6, S5, OS4, NS4, and S4 donor sets. Syntheses, properties, and x-ray structure determinations of [Ni('S6')], [Ni('S5')], [Ni('OS4')]2, [Ni('S4-C5')]2, and [Ni('S4-C3')]. Inorganic Chemistry 29, 4772-4778, (1990).
6 Sellmann, D., Blum, David C. F., Heinemann, Frank W. & Sutter, J. Synthesis, Structure and Reactivity of Sulfur-Rich [Fe(L1)(L2)(‘tpS4’)] Complexes with Rigid [Fe(‘tpS4’] Cores and σ−π Co-Ligands (‘tpS4’2− = 1,2-Bis(2-mercaptophenylthio)phenylene(2−); L1, L2 = CO, PR3, NO). European Journal of Inorganic Chemistry 2003, 418-426, (2003).
7 Sellmann, D., Soglowek, W., Knoch, F., Ritter, G. & Dengler, J. Transition-metal complexes with sulfur ligands. 88. Dependence of spin state, structure, and reactivity of [FeII(L) ('NH)S4')] complexes on the coligand L (L = CO, N2H2, N2H4, NH3, pyridine, NHCH3NH2, CH3OH, THF, P(OCH3)3, P(OPh)3): model complexes for iron nitrogenases ('NHS4'2-dianion of 2,2'-bis[(2-mercaptophenyl)thio]diethylamine). Inorganic Chemistry 31, 3711-3717, (1992).
8 Sellmann, D., Utz, J. & Heinemann, F. W. Transition-Metal Complexes with Sulfur Ligands. 132.1 Electron-Rich Fe and Ru Complexes with [MN2S3] Cores Containing the New Pentadentate Ligand ‘N2H2S3‘2- (= 2,2‘-Bis(2-mercaptophenylamino)diethyl Sulfide(2−)). Inorganic Chemistry 38, 459-466, (1999).
9 C. Davies, S. et al. Vanadium complexes of the N(CH2CH2S)33- ligand with co-ligands relevant to nitrogen fixation processes. Chemical Communications, 1261-1262, (1997).
10 C. Davies, S., L. Hughes, D., L. Richards, R. & Roger Sanders, J. Iron complexes of the N(CH2CH2S)33- ligand; a paramagnetic, trigonal bipyramidal Fe(II) CO complex as a chelate ligand. Chemical Communications, 2699-2700, (1998).
11 Davies, S. C., Hughes, D. L., Richards, R. L. & Sanders, J. R. Molybdenum and tungsten complexes of the N(CH2CH2S)33- (NS3) ligand with oxide, sulfide, diazenide, hydrazide and nitrosyl co-ligands. Journal of the Chemical Society, Dalton Transactions, 719-725, (2000).
12 Takaoka, A., Mankad, N. P. & Peters, J. C. Dinitrogen complexes of sulfur-ligated iron. J Am Chem Soc 133, 8440-8443, (2011).
13 Chu, W.-C., Wu, C.-C. & Hsu, H.-F. Catalytic Reduction of Hydrazine to Ammonia by a Vanadium Thiolate Complex. Inorganic Chemistry 45, 3164-3166, (2006).
14 Issleib, K. & Gans, W. Cobalt- sowie Rhodiumkpmplexe primarer Mercaptoalkyl-phosphine und Bemerkungen zur Komplexbildung quadridentater P,P,S,S-liganden. Z. Anorg. Allg. Chem 491, 163-174, (1982).
15 Schmelzer, R. S. D. Meso and Racemic diastereoisomers of 1,3-bis(2-mercaptoethyl-phenyl-phosphino)-propane nickel (II). Cryst. Struct. Commun. 10, 1317-1321, (1981).
16 Champness, N. R., Frampton, C. S., Reid, G. & Tocher, D. A. Mixed phosphathia macrocyclic chemistry: synthesis and characterisation of [M(Ph2[14]ane P2S2)]2+(M = Pd or Pt) and [RhCl2(Ph2[14]ane P2S2)]+(Ph2[14]ane P2S2= 8, 12-diphenyl-1, 5-dithia-8, 12-diphosphacyclotetradecane). Journal of the Chemical Society, Dalton Transactions, 3031-3037, (1994).
17 Kitajima, N., Fujisawa, K. & Morooka, Y. Tetrahedral copper(II) complexes supported by a hindered pyrazolylborate. Formation of the thiolato complex, which closely mimics the spectroscopic characteristics of blue copper proteins. Journal of the American Chemical Society 112, 3210-3212, (1990).
18 Ohta, T. et al. Synthesis, Structure, and H2O2-Dependent Catalytic Functions of Disulfide-Bridged Dicopper(I) and Related Thioether−Copper(I) and Thioether−Copper(II) Complexes. Inorganic Chemistry 39, 4358-4369, (2000).
19 Houser, R. P., Young, V. G. & Tolman, W. B. A Thiolate-Bridged, Fully Delocalized Mixed-Valence Dicopper(I,II) Complex That Models the CuA Biological Electron-Transfer Site. Journal of the American Chemical Society 118, 2101-2102, (1996).
20 Gennari, M. et al. A fully delocalized mixed-valence bis-mu(thiolato) dicopper complex: a structural and functional model of the biological CuA center. Angewandte Chemie 50, 5662-5666, (2011).
21 Rammal, W. et al. Multifrequency EPR and Redox Reactivity Investigations of a Bis(μ-thiolato)-dicopper(II,II) Complex. Inorganic Chemistry 45, 10355-10362, (2006).
22 Fernández, P. et al. Synthesis and Structural Characterization of Cobalt, Nickel and Copper Phosphanylthiolato Complexes. European Journal of Inorganic Chemistry 2010, 814-823, (2010).
23 Noda, K. et al. Syntheses and first structural analyses of Cu(I)–PS complexes with bidentate 1,1-diphenyl-1-phospha-4-thiapentane (mtdpp) and quadridentate 5,9-diphenyl-5,9-diphospha-2,12-dithiatridecane (2,3,2-SPPS): successful synthetic route for monomeric [Cu(mtdpp)2]BF4 and dimeric [Cu2(2,3,2-SPPS)2](BF4)2. Inorganica Chimica Acta 357, 526-532, (2004).
24 Genge, A. R. J., Gibson, A. M., Guymer, N. K. & Reid, G. Structural and spectroscopic studies on copper, silver and gold complexes of mixed phosphathia ligands and their chalcogenide derivatives. Journal of the Chemical Society, Dalton Transactions, 4099-4107, (1996).
25 Chen, P. W. Development of tetradendate thiolatophosphine ligands: Syntheses and characterization of dithiolate-diphosphine ligands. 國立成功大學化學研究所碩士論文, (2012).
26 Hong, R. N. Development of tetradentate thiolatophosphine ligands and their metal complexes: Syntheses and Characterization of cadmium(II) and lead(II) complexes. 國立成功大學化學研究所碩士論文, (2013).
27 Umemoto, T. & Ishihara, S. Effective methods for preparing S-(trifluoromethyl)dibenzothiophenium salts. Journal of Fluorine Chemistry 92, 181-187, (1998).
28 Long, R. J., Jones, D. J., Gibson, V. C. & White, A. J. P. Zirconium Complexes Containing Tetradentate O,P,P,O Ligands: Ethylene and Propylene Polymerization Studies. Organometallics 27, 5960-5967, (2008).

校內：2019-08-07公開
校外：2019-08-07公開

簡易檢索 / 詳目顯示

相關論文