臺灣博碩士論文加值系統

為了要了解在多硫配位環境下的釩金屬化學，我們使用了PS2 配位基 (PS2= PhPS2H、PhPS2”以及tBuPS2H)、PS1 配位基 (PS1= PS1H、PS1’以及PS1”) 以及 SiS3 配位基 (SiS3 =MeSiS3H 以及HSiS3’) 與釩金屬化合物進行反應。這些反應形成了三種不同類型的釩硫錯合物，分別為非含氧單核三/四價釩硫化合物，雙核含氧四價釩硫化合物，多核三/四價釩硫化合物。
在第一部份，我們得到了化合物 [VIII(PhPS2H)2]-(I-1)，[VIII(PhPS2”)2]-(I-2)，[VIII(tBuPS2H)2]-(I-3)，[VIV(PhPS2H)2] (I-4)，[VIV(PhPS2”)2] (I-5)，[VIII(PS1H)3] (I-6)，[VIII(PS1’)3] (I-7) 以及 [VIII(PS1”)3] (I-8)。化合物 I-1 – I-5 具有 P2S4 配位環境,而化合物 I-6 – I-8 具有 P3S3 配位環境，這些化合物的幾何結構根據它們的結構參數可以分成兩類：八面體以及三角柱。其中唯一例外的是化合物 I-5 具有三角柱結構，其它的化合物都是屬於八面體的幾何結構。
在第二部份， 我們討論了兩個雙核含氧四價釩硫化合物，[VIVO(CH3)SiO(C6H4-2-S)2]22-(II-1) 以及 [(VIVO(C6H5)PO(C6H4-2-S)2)2(MeO)]-(II-2)。這兩個化合物都具有 [VO(μ-OR)2VO]2+ 中心並且屬於syn-orthogonal 的幾何形狀，從磁性測量結果發現在兩個釩金屬中心具有鐵磁性偶合作用力。我們推測這個鐵磁性交互作用力是來自於兩個磁性軌域 (dxy) 的微弱重疊，並且是與兩個釩金屬平面雙面角 (dihedral angle) 過小有關。
在最後章節，我們得到兩個多核三/四價釩硫化合物[V3Cl2{(CH3)Si(C6H4-2-S)3}3](III-1) 以及 [V4Cl{(CH3)Si(C6H4-2-S)3}4]- (III-2)，除此之外，我們也討論了兩個新的釩硫化合物， [V{Si(CH3(5-Me-C6H4- 2-S)CN)(5-Me-C6H4-2-S)2}2]- (III-3) 以及[V{SiO(5-Me-C6H4-2-S)3}]22- (III-4)。
這本論文中，我們會詳細敘述這些化合物的合成方式、結構特性、磁性性質、電化學特性以及光譜性質

In our efforts to understand the chemistry of vanadium complexes in S-rich ligation environment, we have utilized PS2 ligands (PS2= PhPS2H, PhPS2” and tBuPS2H), PS1 ligands (PS1= PS1H, PS1’ and PS1”), and SiS3 ligands (SiS3 =MeSiS3H and HSiS3’) to react with vanadium ion. The reactions led to the formation of three types of vanadium thiolate compounds. They are non-oxo monuclear VIII/IV thiolate complexes, dinuclear oxo VIV thiolate complexes and multinuclear VIII/IV thiolate clusters.
The isolated compounds for the first type are [VIII(PhPS2H)2]-(I-1), [VIII(PhPS2”)2]-(I-2), [VIII(tBuPS2H)2]- (I-3), [VIV(PhPS2H)2] (I-4), [VIV(PhPS2”)2] (I-5), [VIII(PS1H)3] (I-6),[VIII(PS1’)3] (I-7), [VIII(PS1”)3] (I-8). Complexes I-1 – I-5 have P2S4 donor set and complexes I-6 – I-8 have P3S3 ligantion environment. The geometries adopted for most of these compounds should be considered between two limits, octahedron and trigonal prism, according to their structural parameters. Exceptional one is complex I-5 that has a geometry closed to an ideal trigonal prism.
In the second type, we reported two dinuclear oxo VIV thiolate complexes, [VIVO(CH3)SiO(C6H4-2-S)2]2 2- (II-1), [(VIVO(C6H5)PO(C6H4-2-S)2)2(MeO)]- (II-2). These two complexes have the [VO(μ-OR)2VO]2+ core unit in a syn-orthogonal arrangement and display ferromagnetic coupling interaction between vanadyl ions. We propose that this ferromagneric coupling interaction is likely due to the small dihedral angle between two basal planes, leading to the poor overlap of two dxy orbitals.
In the last section, we obtained two multinuclear VIII/IV thiolate clusters, [V3Cl2{(CH3)Si(C6H4-2-S)3}3] (III-1) and [V4Cl{(CH3)Si(C6H4-2-S)3}4]- (III-2). In addition, we also got two vanadium thiolate compounds, [V{Si(CH3(5-Me- C6H4-2-S)CN)(5-Me-C6H4-2-S)2}2]-(III-3) and [V{SiO(5-Me- C6H4-2-S)3}]2 2- (III-4).
In this dissertation, we detail the syntheses, structures, magnetic properties, electrochemical behavior and spectroscopic features of these complexes, as well as their significance.

中文摘要................................................I
ABSTRACT...............................................II
謝誌...................................................III
TABLE OF CONTENTS......................................IV
List of Figures........................................VI
List of Tables.........................................X
Chapter 1: Backgrounds.................................1
Part I: Biological inspiration of vanadium thiolate chemistry..............................................1
Part II: Studies of Non-oxovanadium complexes..........2
Part III: Studies of Dinuclear metal complexes.........5
Part IV: Studies of Multinuclear vanadium complexes....18
Chapter 2: Results and Discussion of Mononuclear six-coordinated nonoxovanadium(III/IV) thiolate complexes..20
Part I: Bis(PS2) non-oxovanadium(III/IV) thiolate complexes. (Preparation, St ructural proper t ies, Spect roscopic , Magnet ic chemist ry and Electrochemistry characterizations of Complexes I-1, I-2, I-3, I-4 and I-5)...................................................22
Preparation of Complexes I-1, I-2, I-3, I-4 and I-5 ...22
Structural properties of Complexes I-1, I-2, I-3, I-4 and I-5................................................23
Spectroscopic characterizations of Complexes I-1, I-2, I-3, I-4 andI-5........................................31
Magnetic chemistry of Complexes I-1, I-2 and I-3.......32
Electron paramagnetic resonance measurements of Complexes I-4 and I-5..................................33
Electrochemistry of Complexes I-1, I-2, I-3, I-4 and I-5....................................................36
Part II: Tris(PS1) vanadium(III) thiolate complexes.(Preparation, Structural properties, Spectroscopic and Electrochemistry characterizations of Complexes I-6, I-7 and I-8)...............................................39
Preparation of Complexes I-6, I-7 and I-8 .............39
Structural properties of Complexes I-6, I-7 and I-8....39
Spectroscopic characterizations of Complexes I-6, I-7 and I-8................................................45
Electrochemistry of complexes I-6, I-7 and I-8.........45
Chapter 3: Results and Discussion of Dinuclear oxovanadium(IV) thiolate complexes................................48
Part III: Dinuclear oxovanadium(IV) thiolate complexes (Preparation, Structural properties and Spectroscopic characterizations of Complexes II-1 and II-2 ).........49
Preparation of Complexes II-1 and II-2.................49
Structural properties of Complexes II-1 and II-2.......49
Spectroscopic characterizations of Complexes II-1 and II-2...................................................55
Structure comparison of Complexes II-1 and II-2........57
Part II: Correlation between structure and magnetic chemistry of dinuclear oxovanadium(IV) complexes.......60
Chapter 4: Results and Discussion of Multinuclear vanadium thiolate complexes............................67
Part I: Preparation and Structural properties of Complexes III-1, III-2, III-3 andIII-4.................69
Preparation of Complexes III-1, III-2, III-3 and III-4...........................69
Molecular structures of Complexes III-1, III-2, III-3 and III-4..................................................70
Part II: Spectroscopic and Magnetic-chemistry characterizations of Complexes III-1...................80
Spectroscopic characterizations of Complex III-1.......80
Magnetic chemistry of Complex III-1....................81
Chapter 5: Conclusion..................................82
Chapter 6: Experiments and Instruments.................83
General Procedures................................... .83
Part I: Preparation of Complexes I-1, I-2, I-3, I-4, I-5, I-6, I-7 and I-8..................................84
Part II: Preparation of Complexes II-1 and II-2........90
Part III: Preparation of Complex III-1.................93
REERFENCE..............................................97

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