過度金屬與具有生物活性的含硫配位基像半胱胺酸及穀胱甘肽之間的作用，在對於生物學或醫學領域上都是不可或缺的議題。因此，我們致力於了解釩金屬與具有仿生物活性的含硫配位基之間的化學現象。此外，有機硫化物的氧化反應在化學燃料、生物學及醫學領域上是個非常有趣的課題，所以在這份研究當中，我們主要的研究方向著重在釩硫化學及有機硫化物的催化氧化作用上。
第一部分，我們成功的合成出六個非含氧基釩硫化合物，分別為[PPh4]2[VIV2(PS3)2(µ-Se2)(µ-Se)] (1)、 [VV2(PS3”)2(µ-Se2)(µ-Se)] (2)、 [VV2(PS3”)2(µ-S2)(µ-S)] (3a)、[VV2 (PS3)2(µ-S2)(µ-S)] (3b)、[PPh4][VIV2(PS3”)2(μ-OMe)3] (4)和 [PPh4][VIV(PS3”)(η2-Se2)] (5) ([PS3]3 = [P(C6H4-2-S)3]3PS3”]3 = [P(C6H3-3-Me3Si-2-S)3]3)，同時也鑑定這些化合物的固體結構。化合物1, 2, 3a及3b有相似的配位環境，兩個釩金屬中心都是由一個硫族原子及硫族雙原子作為架橋鍵結，形成V2(µ-E)(µ–η2:η2-E2) (E = S or Se)的核心構造。化合物4則的兩個釩金屬中心則是由三個甲氧基作為架橋鍵結，V2(µ-OMe)3的核心構造。化合物1是雙核釩四價化合物，由於兩個d1電子間有強的反鐵磁作用，所以使化合物1為反鐵磁化合物。化合物2、3a及3b三個是存在於釩的最高氧化態，在文獻上少見的雙釩五價化合物，特別是在以硫族原子作為架橋鍵結的雙釩化合物未曾見過的。化合物4則是一個少見的順磁性的例子。在此，我們可以藉由低價釩金屬與硫族原子進行反應而得到高價釩化合物。
第二部分中，利用含有希夫鹼配位基的過渡金屬錯合物來探討催化硫氧化反應，反應的過程是以醇類作為溶劑，而雙氧水則作為氧化劑。在這些試驗當中，最佳的催化硫氧化反應是利用鈦四價與配位基L3c的錯合物作為催化劑：催化甲基(對-甲苯基)硫醚的催化氧化反應速率可以達到每小時87個循環。

The chemistry of transition metal ions binding with sulfur containing bio-ligands such as cysteine and glutathione is an important subject in various biological and medical systems. Thus, efforts have been made on understanding the chemistry of vanadium complexes with thiolate ligands that mimic biological S-donors. In addition, oxidation of organic sulfide compounds is also involved in the refinement of chemical fuels and drug syntheses. Based on these backgrounds, two topics will be studied in this thesis.
At the first part, several non-oxido high-valent vanadium complexes were synthesized and fully characterized. They are [PPh4]2[VIV2(PS3)2(µ-Se2)(µ-Se)] (1), [VV2(PS3”)2(µ-Se2)(µ-Se)] (2). [VV2(PS3”)2(µ-S2)(µ-S)] (3a), [VV2 (PS3)2(µ-S2)(µ-S)] (3b), [PPh4][VIV2(PS3”)2(μ-OMe)3] (4), and [PPh4][VIV(PS3”)(η2-Se2)] (5) ([PS3]3 = [P(C6H4-2-S)3]3PS3”]3 = [P(C6H3-3-Me3Si-2-S)3]3). The structures of complexes (1, 2, 3a and 3b) consist of a similar divanadium motif, in which two metal centers are bridged by one µ-chalcogenide and one µ–η2:η2-dichalcogenide, forming a V2(µ-E)(µ–η2:η2-E2) (E = S or Se) core structure. The structure of complex 4 consists of two metal centers bridged by three µ-methoxide groups, giving a V2(µ-OMe)3 core structure. Compounds 1 and 4 have divanadium(IV) centers, but exhibit different magnetic properties; one shows a diamagnetic behavior indicating a strong antiferromagnetic coupling between two d1 centers and the other displays a paramagnetic nature. Notably, compounds 2 and 3a–b have the highest oxidation states for vanadium ions (+5/+5) among those reported divanadium chalcogenide clusters. The work also demonstrates that high-valent divanadium chalcogenide clusters can be obtained with the activation of elemental chalcogens by low-valent vanadium ions.
At the second part, transition metal complexes of Schiff base ligands were explored for catalytic sulfoxidation. The reactions were run in alcohol solvents with hydrogen peroxide as an oxidant. Among the reactions, Ti4+ complex with ligand L3c (o-xylenylididene-di(amino)-bis(2-deoxy--D-glucopyanose)) has the best catalytic performance; the TOF is 87 h-1 for the sulfoxidation of methyl p-tolylsulfide.

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