臺灣博碩士論文加值系統

The reversible redox transformations [(NO)2Fe(StBu)2]– [Fe(-StBu)(NO)2]22– (2) [Fe(-StBu)(NO)2]2– [Fe(-StBu)(NO)2]2 are demonstrated. The binding preference of ligands [OPh]–/[SR]– toward the {Fe(NO)2}10-{Fe(NO)2}10 motif of dianionic reduced RRE follows the ligand-displacement series [SR]–＞[OPh]–, rationalizing that most of the DNICs and RREs characterized nowadays are bound to protein via cysteinate side chains. Compared to the Fe K-edge pre-edge energy falling within the range of 7113.6-7113.8 eV for the dinuclear {Fe(NO)2}9-{Fe(NO)2}9 DNICs and 7113.4-7113.8 eV for the mononuclear {Fe(NO)2}9 DNICs, the {Fe(NO)2}10 reduced DNICs and the {Fe(NO)2}10-{Fe(NO)2}10 dianionic reduced RREs containing S-/O-/N-ligation modes display the characteristic pre-edge energy 7113.1-7113.3 eV, which may be adopted to probe the formation of the EPR-silent {Fe(NO)2}10-{Fe(NO)2}10 dianionic reduced RREs and {Fe(NO)2}10 dianionic reduced monomeric DNICs in biology. In addition to the characteristic Fe/S K-edge pre-edge energy, the IR νNO spectra may also be adopted to characterize and discriminate [(NO)2Fe(-StBu)]2 (IR νNO 1809 vw, 1778 s, 1753 s cm-1 (KBr)), [Fe(-StBu)(NO)2]2– (IR νNO 1674 s, 1651 s cm-1 (KBr)), and [Fe(-StBu)(NO)2]22– (IR νNO 1637 m, 1613 s, 1578 s, 1567 s cm-1 (KBr)). Additionally, The fluxional terminal and semibridging NO-coordinate ligands of DNIC [Fe4(-S)2(-NO)2(NO)6]2– (3), a precursor of Roussin’s black salt (RBS), are characterized by IR NO), 15N(NO) NMR, single-crystal X-ray diffraction, and DFT calculations. Compared to the {Fe(NO)2}9 and {Fe(NO)2}10 DNICs/RREs displaying 15N (NO) NMR chemical shift (23 ~ 76 ppm) and (-7.8 ~ 25 ppm), respectively, the first semibridging nitroxyl of complex 3 exhibits the distinct 15N (NO) NMR chemical shift (200.8 and 200.1 ppm), suggesting the 15N (NO) NMR technique can serve as an efficient tool to discriminate the binding fashions of NO. In the last part, the stable {Fe(NO)2}10 reduced DNICs [(NO)2Fe(S(CH2)nS)]2– [ n = 3 (4); n = 2 (5) ] containing chelate dithiolate were synthesized. On the basis of the electrochemistry, and DFT calculations of 4 and 5, the bite angle or ring strain inherent in the chelate-dithiolate-bound DNICs will function to tune the Fe-S bonding level, so as to modulate the configurations and electrochemical properties of DNICs (E1/2 = -1.64 V for 4 and E1/2 = -1.33 V for 5). The dithiolate ligands are also introduced to build [(NO)2Fe(-2-SC2H4S)(-NO)Fe(NO)]2– (7) bearing a bridging NO as well as the fluxional isomers of [(NO)2Fe(-2-SC3H6S)(-NO)Fe(NO)]2– (8-a) and [(NO)2Fe(-SC3H6S)Fe(NO)2]2– (8-b). Intriguingly, the electrochemical studies demonstrate that complex 7, resembling to the calculated double-reduced intermediate [(CO)3Fe(-2-edt)(-CO)Fe(CO)2]2– of [FeFe]-H2ase model, act as an active molecular electrocatalyst for proton reduction from weak acid with low overpotential.

Table of Contents
I. CHAPER ONE INTRODUCTION 1
1. Nitric Oxide 1
1-1. Biosynthesis of Nitric Oxide 1
1-2. NO storage and delivery 3
1-3. NO-regulated biofunctions 7
2. Bioinspired Chemistry: Dinitrosyliron Complex (DNIC) 13
3. [Fe-Fe]-Hydrogenase 19
II. CHAPTER TWO EXPERIMENTAL SECTION 26
General. 26
Synthesis of [PPN]2[Fe(-OPh)(NO)2]2 (1) 27
Reaction of complex 1 and [K-18-crown-6-ether][StBu] yielding [PPN]2[Fe(-StBu)(NO)2]2 (2) 27
Reaction of [PPN][(NO)2Fe(StBu)2] and 1 equiv of KC8 yielding [PPN]2[Fe(-StBu)(NO)2]2 (2) 28
Reaction of [PPN][(NO)2Fe(StBu)2] and 0.5 equiv of KC8 affording [PPN][Fe(-StBu)(NO)2]2 (rRRE-StBu) 29
Reaction of [PPN][Fe(-StBu)(NO)2]2 (rRRE-StBu) and KC8 yielding [PPN]2[Fe(-StBu)(NO)2]2 (2) 29
Preparation of [K-18-crown-6-ether]2[Fe4(-S)2(-NO)2(NO)6] (3) 30
Reaction of Complex 3, [Cp2Fe][BF4] and HSCPh3 30
Reaction of [K-18-crown-6-ether][(NO)2Fe(S(CH2)3S)] and 1 equiv of [KC8]+[18-crown-6-ether] affording [K-18-crown-6-ether]2[((NO)2Fe(S(CH2)3S)] (4) 31
Preparation of [PPN]2[(NO)2Fe(S(CH2)2S)] (5) and [K-18-crown-6-ether]2[(NO)2Fe(S(CH2)2S)] (5-CrownK) 32
Preparation of [K-18-crown-6-ether]2[(NO)2Fe(-SC2H4S)2Fe(NO)2] (6) 33
Preparation of [PPN]2[(NO)2Fe(-2-SC2H4S)(-NO)Fe(NO)] (7) 33
Preparation of [PPN]2[(NO)2Fe(-2-SC3H6S)(-NO)Fe(NO)] (8-a) and [PPN]2[(NO)2Fe(-SC3H6S)Fe(NO)2] (8-b) 34
Preparation of [PPN]2[(NO)2Fe(-2-bdt)(-NO)Fe(NO)] (9) and [K-18-crown-6-ether]2[(NO)2Fe(-2-bdt)(-NO)Fe(NO)] (9-CrownK) (bdt = 4-methyl-1,2-benzenedithiolate) 35
Magnetic Measurements 35
Magnetic Susceptibility 36
Electrochemistry 37
Computational Details 38
X-ray Absorption Measurements 39
Crystallography 40
III. CHAPER THREE RESULTS AND DISCUSSION 51
Part I: Insight into the redox transformation and electronic structure of {Fe(NO)2}10-{Fe(NO)2}10 dianionic reduced RRE 51
Part II: Iron-sulfur nitrosyl complex [Fe4(-S)2(-NO)2(NO)6]2–: 15N (NO) NMR analysis of the terminal and bridging NO-coordinate ligands. 59
Part III: Chelating dithiolate governing the configuration and electrochemical properties of dinitrosyliron complexes (DNICs): potential for electrocatalytic proton reduction. 71
Part IV: X-ray Absorption Spectroscopy (XAS). 98
IV CHAPTER FOUR CONCLUSION AND COMMENTS 108
References 116

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