含鎳/鐵金屬之生化擬態模型化合物的研究：鎳/鐵氫化酵素和鐵醯腈水解酵素

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研究生：	李建明 LEE CHIEN-MING
論文名稱：	含鎳/鐵金屬之生化擬態模型化合物的研究：鎳/鐵氫化酵素和鐵醯腈水解酵素 Biomimetic Model Studies on Ni/Fe-Containing Metalloenzymes: [NiFe] Hydrogenase and Fe-Containing Nitrile Hydratase
指導教授：	廖文峯 LIAW WEN-FENG
口試委員:
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2005
畢業學年度：	93
語文別：	英文
中文關鍵詞：	生化擬態模型化合物、鎳/鐵氫化酵素、鐵醯腈水解酵素
外文關鍵詞：	Biomimetic Model, Ni/Fe-Containing Metalloenzymes, [NiFe] Hydrogenase, Fe-Containing Nitrile Hydratase
相關次數：	點閱：2 下載：0
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單核平面四方形結構的化合物 [NiII(SePh)(P(o-C6H3RS)2(o-C6H3RSH))]- (R = H (I-1), SiMe3 (II-la or II-lb)) 具有一個硫醇官能基，硫醇官能基上的質子同時和分子內的硫原子與鎳原子產生交互作用(type I)或質子單獨和鎳原子產生交互作用(type II)，可以由化合物[Ni(CO)(SePh)3]- 和化合物P(o-C6H4SH)3/ P(C6H3-3- SiMe3-2-SH)3 分別反應而產生。藉由紅外線光譜學、核磁共振光譜及單晶X光繞射結構解析的研究，證明此特殊分子內作用力的存在 (表4-1)。由氘同位素水分子與硫醇官能基上氫質子的交換實驗，配合紅外線光譜學、核磁共振光譜，亦證明硫醇官能基上氫質子的存在。在氧氣的環境下化合物 [NiII(SePh)(P(o-C6H3- RS)2(o-C6H3RSH))]- (R = H (I-1), SiMe3 (II-la or II-lb))會分別轉換成化合物 [NiIII (SePh)(P(o-C6H3RS)3)]- (R = H (I-2)，SiMe3 (II-2))和H2O。化合物II-2可以當作一個好的起始物。在CO環境下，化合物II-2可以轉換成化合物 [NiII(CO) (P(C6- H3-3-SiMe3-2-S)3)]- (II-3)或可以與CH2Cl2反應產生化合物[NiIII(Cl)(P(C6H3-3- SiMe3-2-S)3)]- (II-4)。化合物II-4亦可以當作一個好的起始物去合成 [NiIII(SEt)(P- (C6H3-3-SiMe3-2-S)3)]- (II-5)。此外，化合物[Ni(Cl)(P(C6H3-3-Si-Me3-2-S)2(C6H3-3- SiMe3-2-SH))] (II-6)、[Ni(P(C6H3-3-SiMe3-2-S)(C6H3-3-SiMe3-2-SH)(C6H3-3-SiMe3- 2-□-S))]2 (II-7) 和[NiIII(P(C6H3-3-SiMe3-2-S)2 (C6H3-3-SiMe3-2-□-S))]2 (II-8)可以被合成出來，藉由探討這些化合物的電子結構、幾何結構、光譜特性和反應機制，可以對鎳鐵-氫化酵素的特性做有意義的解釋。
五配位鐵-硫-硝基化合物[(NO)Fe(S,S-C6H4)2]- (20)和[(NO)Fe(S,S-C6H4)2]2- (III-1)可以成功的被合成出來。具有{Fe(NO)}6電子組態的化合物20可以與氧氣反應產生化合物[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)]- (21)。相反的，化合物III-1與氧氣反應產生化合物20為主要產物、[Fe(S,S-C6H4)2]22- 和 [NO3]- (9％)為副產物。此外，化合物 [(NO)Fe(S,SO2-C6H4)(S,S-C6H4)]2- (III-2) 可由化合物21與[EtS]-反應得到。在氧化反應的比較方面，鍵結電子給予能力較弱的sulfinate配位基的化合物III-2會直接轉換成化合物21。由化合物20-21-III-1-III-2之間的轉變也許可以提供一些訊息，以解釋腈水解酵素在活化態與非活化態之間轉換的機制。

Mononuclear, distorted square planar [NiII(SePh)(P(o-C6H3RS)2(o-C6H3RSH))]- (R = H (I-1), SiMe3 (II-la or II-lb)) with a S－H proton interacting with both nickel and sulfur atoms (Type I) or an intramolecular [Ni…H－S] interaction (Type II) were prepared by reaction of [Ni(CO)(SePh)3]- and P(o-C6H4SH)3/ P(C6H3-3-SiMe3-2-SH)3, respectively. The presence of intramolecular [Ni…H－S]/[Ni－S…H－S] interac- tions was verified in the solid state by the observation of the IR vS－H band (Table 4-1) and subsequently confirmed by X-ray diffraction study. The exo-thiol proton in I-1, II-la and II-lb was identified as a D2O exchangeable proton from NMR and IR stu- dies. Instead of the ligand-base oxidation to form dinuclear Ni(II) complexes and diphenyl diselenide, oxidation of THF-CH3CN solution of I-1, II-la and II-lb by O2 resulted in the formation of the mononuclear, distorted trigonal bipyramidal [NiIII(Se- Ph)(P(o-C6H3RS)3)]- (R = H (I-2), SiMe3 (II-2)) accompanied by byproduct H2O identified by 1H NMR, individually. Importantly, the reversible transformation from [Ni(III)－S] (II-2) to [Ni(II)…H－S] (II-1a or II-1b) was observed by reaction of II-2 and LiAlH4, followed by the addition of H2O (H+ source). More sterically hindered and stable complex II-2 reacts with exogenous CO to produce [NiII(CO) (P(C6H3-3-SiMe3-2-S)3)]- (II-3). Complex II-2 undergoes dechlorination in CH2Cl2 solution to generate [NiIII(Cl)(P(C6H3-3-SiMe3-2-S)3)]- (II-4) which acts as a precur- sor for synthesis of [NiIII(SEt)(P(C6H3-3-SiMe3-2-S)3)]- (II-5) via ligand metathesis. The EPR spectra of I-2, II-2, II-4 and II-5 exhibiting high rhombicities with three principal g values of 2.30, 2.09 and 2.0 are consonant with Ni(III) with the odd elec- tron in the dz2 orbital. The cyclic voltammetric response of I-2, II-2 and II-5 reveals a reversible NiIII/II process (Table 4-1). When II-1 is dissolved in CH2Cl2 at room temperature, a slow reaction ensues to give the mononuclear [Ni(Cl)(P(C6H3-3-Si- Me3-2-S)2(C6H3-3-SiMe3-2-SH))]- (II-6) after separation of dinuclear neutral [Ni(P- (C6H3-3-SiMe3-2-S)(C6H3-3-SiMe3-2-SH) (C6H3-3-SiMe3-2-□-S))]2 (II-7) by diethyl ether. Two types of crystalline products, orange-red plate (II-6a) and red-brown block (II-6b), were isolated upon precipitation of II-6 with different solvent pairs. Com- pared to the vS－H stretching frequencies among complexes II-1a, II-1b, II-6a, II-6b and II-7, the vS－H stretching frequencies are disturbed by changing terminal donor ligand (Table 4-1). Upon injecting O2 into a THF solution of II-7, the neutral dinu- clear [NiIII(P(C6H3-3-SiMe3-2-S)2 (C6H3-3-SiMe3-2-□-S))]2 (II-8) is isolated and iden- tified by single crystal X-ray diffraction studies. Electrochemical studies reveal that II-8 undergoes one-electron reduction to a [Ni(III)Ni(II)] species that is further re- duced to a [Ni(II)Ni(II)] species. Some of those results are relative to the structure, reactivity, and spectroscopic properties of the nickel site of bimetallic Ni－Fe active site of [NiFe]H2ase.
The five-coordinated iron-thiolate nitrosyl complexes [(NO)Fe(S,S-C6H4)2]- (20), and [(NO)Fe(S,S-C6H4)2]2- (III-1) have been isolated and structurally characterized. Iron-thiolate nitrosyl complex 20 containing {Fe(NO)}6 core triggers sulfur oxyge- nation by O2 to yield the S-bonded monosulfinate iron species [(NO)Fe(S,SO2- C6H4)(S,S-C6H4)]- (21). In contrast, there is to a certain extent an attack of O2 on the •NO radical of complex III-1 containing {Fe(NO)}7 core leading to the formation of complex 20 accompanied by the minor products, [Fe(S,S-C6H4)2]22- and [NO3]- (9％). Treatment of 1 equiv of [EtS]- and complex 21 in CH3CN-THF yields [(NO)Fe- (S,SO2-C6H4)(S,S-C6H4)]2- (III-2) along with (EtS)2 identified by 1H NMR. Com- pared to III-1, complex III-2 with the less electron-donating sulfinate ligand coordinated to {Fe(NO)}7 core were oxidized by O2 to yield 21. Obviously, the elec- tronic perturbation of the {Fe(NO)}7 core caused by the coordinated sulfinate in III-2 may serve to regulate the reactivity of III-2 toward O2. The iron-sulfinate nitrosyl species with {Fe(NO)}6/7 core exhibit the photolabilization of sulfur-bound [O] moiety under irradiation. The interconversion between complexes 20, 21, III-1 and III-2 (Scheme 4-3) may provide some clues to the transformation pathways between the active and inactive NO-bound forms of Fe-containing nitrile hydratase (Scheme 4-4).

TABLE OF CONTENTS

List of Figures………………………………………………………………..……… iv
List of Tables…………………………………………...……………………………vii
中文摘要……………………………………………………………………………viii
ABSTRACT……………………………………..………………………………….x
CHAPTER 1: Introduction…………………………………………………………….1
Part I: Hydrogenase………………………………………………………………1
[NiFe] Hydrogenase………………………………………………..……….1
        [NiFeSe] Hydrogenase……………………………………………..……….9
        Model chemistry of [NiFe]H2ase and [NiFeSe]H2ase……………….…….10
    Part II: Nitrile Hydratase…….…………………………………...….………….19
        Fe-containing Nitrile Hydratase………..……………………………….…19
        Model chemistry of Fe-containing NHase……………..……………….…22
CHAPTER 2: Experiments.…………..…………………………………………...…27
    General Procedures………………………………………………….…….…….27
    Part I: Preparation of I-1 and I-2………………...………………….……….….28
        Preparation of [PPN][Ni(SePh)P((o-C6H4S)2(o-C6H4SH))] (I-1)...……….28
        D/H Exchange for Reaction of Complex I-1 and D2O..……….……….….28
        Reaction of Et3N and Complex I-1….……...………………….………….28
        Preparation of Complex [PPN][Ni(SePh)(P(o-C6H4S)3)] (I-2) .……….….29
        Part II: Preparation of II-1a, II-1b, II-2, II-3, II-4, II-5, II-6a, II-6b, II-7 and
II-8………………………………………………………….……..…….29
Preparation of [PPN][Ni(SePh)P((C6H3-3-SiMe3-2-S)2(C6H3-3-SiMe3-2- SH))] (II-1a) and (II-1b)..…………………………………….……..…….29
D/H Exchange for Reaction of Complex II-1 and D2O……………..…….30
Preparation of [PPN][Ni(SePh)(P(C6H3-3-SiMe3-2-S)3)] (II-2)...…..…….30
Reduction of [PPN][Ni(SePh)(P(C6H3-3-SiMe3-2-S)3)] (II-2) by LiAlH4..31
Preparation of [PPN][Ni(CO)(P(C6H3-3-SiMe3-2-S)3)] (II-3)..…….…….31
Preparation of [PPN][Ni(Cl)(P(C6H3-3-SiMe3-2-S)3)] (II-4)……….…….32
Preparation of [PPN][Ni(SC2H5)(P(C6H3-3-SiMe3-2-S)3)] (II-5).….…….32
Preparation of [PPN][Ni(Cl)P((C6H3-3-SiMe3-2-S)2(C6H3-3-SiMe3-2- SH))] (II-6a) and (II-6b)…………………………………………….……..…….33
Preparation of [NiP((C6H3-3-SiMe3-2-S)2(C6H3-3-SiMe3-2-SH))]2 (II-7)..34
D/H Exchange for Reaction of Complex II-7 and D2O...…….……..…….34
Preparation of [NiP(C6H3-3-SiMe3-2-S)3]2 (II-8).……………….….…….35
Kinetic measurements………………………………..………..…….…….35
Electrochemistry…………………………………………………….…….36
EPR Measurements………………………………………………….…….36
Magnetic Measurements…………………………………………….…….36
Crystallography…………………………………..…….………………….37
    Part III: Preparation of III-1 and III-2 and photolysis studies………………….39
        Preparation of [PPN]2[(NO)Fe(S,S-C6H4)2] (III-1)...….………………….39
        Preparation of [PPN]2[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (III-2)………….39
        Photolysis of CH2Cl2 solution of [PPN][(NO)Fe(S,S-C6H4)2] (20)……….40
Photolysis of CH2Cl2 solution of [PPN][(NO)Fe(SO2,S-C6H4)(S,S-C6H4)] (21) and PPh3………………………………………………………………40
Photolysis of CH3CN solution of [PPN]2[(NO)Fe(S,S-C6H4)2] (III-1)...…40
Photolysis of CH3CN solution of [PPN]2[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (III-2)………………………………………...……………………………40
Reaction of [PPN]2[(NO)Fe(S,S-C6H4)2] (III-1) and O2………………….42
Reaction of [PPN]2[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (III-2) and O2…….42
CHAPTER 3: Results and Discussion……………………………………………….45
    Part I: Preparation and Characterization of I-1 and I-2………………………...45
        Preparation and spectroscopic characterization of complex I-1…………..45
        Specific intramolecular [Ni－S•••H－SR]/[Ni•••H－SR] interaction……...46
        H/D exchange reaction…………………………………………………….48
        Preparation and spectroscopic characterization of complex I-2…………..48
        Molecular structures of complexes I-1 and I-2……………………………52
    Part II: Preparation of II-1a, II-1b, II-2, II-3, II-4, II-5, II-6a, II-6b, II-7 and
II-8………………………………………………………………………55
        Preparation and spectroscopic characterization of complex II-1………….55
        Specific intramolecular [Ni－S•••H－SR]/[Ni•••H－SR] interaction...……58
        H/D exchange reaction…………………………………………………….60
        Molecular structures of complexes II-la and II-lb………...……………...61
        Reaction of complex II-1 with dioxygen………………………………….62
        Reduction of II-2 by LiAlH4……..………………………………………..64
        Reaction of complex II-2 with carbon monoxide…………………………65
        Dechlorination reaction of dichloromethane by complex II-2………….…68
        Reaction of complex II-4 with sodium ethylthiolate……………...………69
        Electronic structures of II-2, II-4 and II-5………………………………..72
        Electrochemistry…………………………………………………………..76
        Molecular structures of complexes II-2, II-3, II-4 and II-5………………77
        Reaction of complex II-1 with CH2Cl2……………………………………82
        The differences between II-6a and II-6b……………………..…………..83
        Molecular structures of complexes II-6a and II-6b………………………87
        Neutral dinuclear Ni(II) complex II-7 with exo-thiol…………………….87
        Reaction of complex II-1 with [Et3O][BF4]………………………………89
        Molecular structures of complexes II-7…………………………………..89
        Reaction of complexes II-6 and II-7 toward molecular oxygen………….91
        Electrochemistry of complex II-8…………………………………………92
        Molecular structures of complexes II-8……………...……………………93
    Part III: Preparation and Characterization of 20, 21, III-1 and III-2…………...96
Spectroscopic evidences of sulfinate (M-SO2R) of [PPN][(NO)Fe(S,SO2- C6H4)(S,S-C6H4)] (21)………………………….………………………….96
Photolysis of [PPN][(NO)Fe(S,S-C6H4)2] (20) by irradiation (Hg lamp, Imax= 366 nm)……………………….……………………………………..98
Conversion studies of [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (21) to [PPN][(NO)Fe(S,S-C6H4)2] (20)…………………………………………..99
Preparation and characterization of complex [PPN]2[(NO)Fe(S,S-C6H4)2] (III-1)………………………… …………………………………………100
Oxidation of III-1 by dioxygen…………………………………………..102
Photolysis of III-1 by irradiation (Hg lamp, Imax= 366 nm)………...……104
Preparation and characterization of complex [PPN]2[(NO)Fe(S,SO2-C6H4) (S,S-C6H4)] (III-2)……………………………………………………….104
        Oxidation of III-2 by dioxygen…………………………………………..106
        Conversion studies of [PPN]2[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (III-2) to
[PPN]2[(NO)Fe(S,S-C6H4)2] (III-1)………………………..…….………107
Molecular structures of complexes III-1 and III-2………………………108
CHAPTER 4: Conclusion and Comments………………...…………….………..…110
    Part I: Complexes I-1, I-2, II-1a, II-1b, II-2, II-3, II-4, II-5, II-6a, II-6b, II-7
and II-8………………………………………..…………………….…110
    Part II: Complexes 20, 21, III-1 and III-2…………………...………………..116
REFERENCE…………………………………………..……………….…………..120
APPENDIX………………………………………………………………………....121








List of Figures


Figure 1-1. The general role of hydrogenases in metabolism………...…………..…...1
Figure 1-2. (a) The small subunit and the large subunit. Reduced form (b) and oxidized form (c) of the active of [NiFe]H2ase isolated from D. gigas at 2.54 Å resolution, where X could be O2- or OH-…………………………2
Figure 1-3. Proposed electron (a) and proton transfer (b) in large and small subunits..4
Figure 1-4. The active-site structure of D. baculatum [NiFeSe]H2ase with the selected bonddistance(Å)…..………….…………………………………………10
Figure 1-5. The crystal structures of the inactive, NO-bound form of iron-type NHase from Rhodococcus sp. N-771……………………...……………………20
Figure 1-6. The possible pathways for the hydroxylation of nitrile in active site……22
Figure 3-1. (a) The IR KBr solid spectra of I-1, and I-1 under H/D exchange reaction with D2O (dash line). (b) Changes in the 2H NMR spectra observed upon the addition of dry O2 into the solution of I-l-SD. The 2H NMR spectra of I-l-SD and I-l-SD upon exposure to dry O2...………………………..…47
Figure 3-2. (a) The UV/vis spectra of complexes I-l and I-2 in CH3CN. (b) EPR spectraum of I-2 frozen in CH2Cl2. (c) Plots of □eff vs T for I-2…….....49
Figure 3-3. ORTEP drawing and labeling scheme of [Ni(SePh)(P(o-C6H4S)2(o-C6H4 -SH))]- (I-1) anion…………………………………………….………...53
Figure 3-4. ORTEP view of [NiIII(SePh)(P(o-C6H4S)3)]- (I-2) anion………………..54
Figure 3-5. The IR spectra of II-1a, II-1b and II-1a under H/D exchange reaction with D2O……………………………..………………….………………56
Figure 3-6. (a) ORTEP drawing and labeling scheme of [Ni(SePh)(P(C6H3-3-SiMe3- 2-S)2(C6H3-3-SiMe3-2-SH))] (II-1a) anion (b) ORTEP view of II-lb anion…………………………………………………………………….57
Figure 3-7. ORTEP views of II-1a (a) and II-1b (b) in a clear drawing to show the differences. (c) A diagram to show the distance between Ni and S atoms in II-1a (Type I) and II-1b (Type II)………………...…………………59
Figure 3-8. Changes in the 2H NMR spectra observed upon the addition of dry O2 into the solution of II-la-SD. The 2H NMR spectra of II-la-SD and II-la-SD exposure to dry O2………………...…………………………………….61
Figure 3-9. Changes in the UV/vis spectra occurred upon the addition of limited O2 into the solution of II-l. (a) The reaction was monitored for 6 cycles (b) The reaction was monitored after 6 cycles………..…………………….64
Figure 3-10. (a) The IR spectrum of II-3 (b) The reaction between II-2 and CO in CH3CN was monitored by UV/vis spectra……………….……….…….66
Figure 3-11. The dechlorination reaction of II-2 and CH2Cl2 monitored by UV/vis spectra.…………………………………………….……………….…...68
Figure 3-12. The UV/vis spectra (in CH3CN) of II-2, II-3 and II-4, respectively. Only two intense absorptions were labeled for comparison……………...…..70
Figure 3-13.(a) The 1H NMR spectra of [Ni(Cl)(P(C6H3-3-SiMe3-2-S)3)]- (II-4), (b) [Ni(SePh)(P(C6H3-3-SiMe3-2-S)3)]- (II-2) and (c) [Ni(SEt)(P(C6H3- 3-SiMe3-2- S)3)]- (II-4) in CD3CN…………………………...…….…..71
Figure 3-14. Kinetics data (circle) and fits (solid line) for the reactions of (a) II-2 with CH2Cl2 (kobs = (4.78 ± 0.02) × 10-5 s-1, R2 = 0.9990) and (b) II-5 with CH2Cl2 (kobs = (6.01 ± 0.03) × 10-4 s-1, R2 = 0.9990)……………......…73
Figure 3-15. (a) 77 K EPR spectra of [Ni(SePh)(P(C6H3-3-SiMe3-2-S)3)]- (II-2), [Ni(Cl)(P(C6H3-3-SiMe3-2-S)3)]- (II-4)) and [Ni(SEt)(P(C6H3-3- SiMe3-2-S)3)]- (II-5) (b) Plots of □eff vs T for II-2 and for II-4)……....74
Figure 3-16. (a) The cyclic voltammograms of [Ni(SePh)(P(o-C6H4S)3)]- (I-2), Ni(SePh)(P(C6H3-3-SiMe3-2-S)3)]- (II-2) and [Ni(SEt)(P(C6H3-3- SiMe3-2-S)3)]- (II-5). (b) The cyclic voltammograms of [Ni(CO)(P(C6H3 -3-SiMe3-2-S)3)]- (II-3) (dashed line) and [Ni(Cl)(P(C6H3-3-SiMe3-2- S)3)]- (II-4)…………………………………………………...…...........75
Figure 3-17. ORTEP drawing and labeling scheme of [Ni(SePh)(P(C6H3-3-SiMe3-2- S)3)] (II-2) anion……………………………………………………….78
Figure 3-18. ORTEP drawing and labeling scheme of [Ni(CO)(P(C6H3-3-SiMe3-2- S)3)] (II-3) anion…………………………………….………....……....79
Figure 3-19. ORTEP drawing and labeling scheme of [Ni(Cl)(P(C6H3-3-SiMe3-2- S)3)] (II-4) anion……………………………………………..………...……..80
Figure 3-20. ORTEP drawing and labeling scheme of [Ni(SC2H5)(P(C6H3-3-SiMe3-2- S)3)] (II-5) anion…………………………………………….………….81
Figure 3-21. (a) ORTEP drawing and labeling scheme of [Ni(Cl)(P(C6H3-3-SiMe3-2- S)2(C6H3-3-SiMe3-2-SH))] (II-6a) anion (b) ORTEP view of II-6b anion. A diagram to show the distance between Ni and S atoms in II-6a (Type I) and II-6b (Type II)…………………………….………………………..85
Figure 3-22. The IR (KBr solid) spectra of II-6a, II-6b……………………………..86
Figure 3-23. The IR (KBr solid) spectra of II-7 and II-7 under H/D exchange reaction with D2O………………….………………………………….…………88
Figure 3-24. ORTEP drawing and labeling scheme of [Ni(P(C6H3-3-SiMe3-2-S) (C6H3-3-SiMe3-2-SH)(C6H3-3-SiMe3-2-□-S))]2 (II-7) anion….….……90
Figure 3-25. The cyclic voltammograms of [NiIII(P(C6H3-3-SiMe3-2-S)2(C6H3-3- SiMe3-2-□-S))]2 (II-8). The dashed line shows the same condition of II-8, but different scan range (0 to -1.0 V).…………………………..……...93
Figure 3-26. ORTEP drawing and labeling scheme of [Ni(P(C6H3-3-SiMe3-2-S)2 (C6H3-3-SiMe3-2-□-S))]2 (II-8) anion………………….……………....94
Figure 3-27. (a) The UV/vis spectra of complexes 20 and 21. (b) The IR spectra (KBr, pellet) of 20 and 21…………………………………..…....…………....97
Figure 3-28. Changes in the UV/vis spectra occurred upon irradiating the solution of 20…………………………………………………..…………………...98
Figure 3-29. Changes in the UV/vis spectra occurred upon irradiating the solution of 21…………………………………………………...………………......99
Figure 3-30. (a) Comparison of the UV/vis spectra of [PPN][(NO)Fe(S,S-C6H4)2] (20) and [PPN]2[(NO)Fe(S,S-C6H4)2] (III-1). (b) The IR spectrum (KBr, pellet) of III-1……………………..…….………….………………...101
Figure 3-31. Changes in the UV/vis spectra occurred upon the addition of limited O2 into the solution of III-l …………………………………….….….….103
Figure 3-32. Comparison of the UV/vis spectra of III-1 after photolysis by Hg lamp (Imax= 366 nm)……….…………………………………………..…....103
Figure 3-33. The Infrared spectrum of [PPN]2[(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (III-2) (KBr pellet)…………………………………………..……….……….105
Figure 3-34. Changes in the UV/vis spectra occurred upon the addition of limited O2 into the solution of III-2………………………...…..…….…………..106
Figure 3-35. Change of the UV/vis spectra of III-2 after photolysis by Hg lamp (Imax= 366 nm)…………………………………………………..…………....107
Figure 3-36. ORTEP drawing of the [(NO)Fe(S,S-C6H4)2]2- (III-1) anion…………109
Figure 3-37. ORTEP drawing of the [(NO)Fe(S,SO2-C6H4)(S,S-C6H4)]2- (III-2) anion…………………………………..………………………….…...109














List of Tables


Table 1-1. Selected bond distances and angles of the active site of [NiFe]H2ase……..3
Table 1-2. Activities mediated by [NiFe]H2ase………………………………………..5
Table 2-1. The parameter lists of X-band EPR spectra of I-2, II-2, II-4 and II-5…...36
Table 2-2. Crystallographic data of complexes I-1 and I-2…………………………..37
Table 2-3. Crystallographic data of complexes II-2and II-3………………...............38
Table 2-4. Crystallographic data of complexes II-4and II-5………………………...38
Table 2-5. Crystallographic data of complexes II-7and II-8………………………...39
Table 2-6. Crystallographic data of complexes III-1 and III-2……………………...43
Table 3-1. Selected bond distances and angles of [Ni(SePh)(P-(o-C6H4S)2(o-C6H4S- H))]- (I-1)……………………………………………………..…………..53
Table 3-2. Selected bond distances and angles of [NiIII(SePh)(P(o-C6H4S)3)]- (I-2)...54
Table 3-3. Crystallographic data of complexes II-1a and II-1b……………………..56
Table 3-4. Selected bond distances and angles of II-1a and II-1b…………………..59
Table 3-5. Selected bond distances and angles of II-2……………………………….78
Table 3-6. Selected bond distances and angles of II-3……………………………….79
Table 3-7. Selected bond distances and angles of II-4……………………………….80
Table 3-8. Selected bond distances and angles of II-5……………………………….81
Table 3-9. Crystallographic data of complexes II-6a and II-6b……………………..84
Table 3-10. Selected bond distances and angles of II-6a and II-6b…………………85
Table 3-11. Selected bond distances and angles of II-7……………………………...90
Table 3-12. Selected bond distances and angles of II-8……………………………...94
Table 3-13. Comparison of structural parameters of five-coordinated {FeNO}6,7 complexes, inactive NHase and its vNO stretching frequencies………108
Table 4-1. Comparison of structural and spectroscopic parameters in the series of I-l to I-2 and II-1 to II-8………………………………………..………….110

                                

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