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Study on the reactivity of dinuclear platinum (III) complexes

双核铂(III)配合物的反应活性研究

基本信息

批准号：
12640542
负责人：
UMAKOSHI Keisuke
金额：
$ 2.3万
依托单位：
Nagasaki University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640542/
关键词：
platinum hydrogenolysis catalytic reaction pyridinethiol C-S bond cleavage 水素化反応

项目摘要

The number of studies on the reactivity and functionality of dinuclear platinum(III) complexes is limited. In order to elucidate the reactivity of dinuclear Pt(III) complexes, we studied the reaction of 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex with H_2 and hydrogenolysis of pyridine-2-thiol in the presence of 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex as a catalyst. Following results were obtained :(1) When 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex reacted with hydrogen in DMF at 150ーC, the C-S bond cleavage of the bridging ligands occurred to liberate 3-picoline. The amount of the liberated picoline increased with increasing applied hydrogen pressure.(2) The catalytic activity of the 5-methylpyridinethiolatobridged dinuclear Pt(III) complex toward C-S bond cleavage of pyridine-2-thiol was examined. The catalytic activity of the Pt(III) complex is higher than that of the corresponding Pt(II) complex.(3) The catalytic activity of the Pt(III) complex depends on the kinds of axial ligand, and it decreases in the order of Cl > Br > I.(4) ^1H NMR study on the hydrogenolysis of pyridinethiol under D_2 atmosphere revealed the formation of deuterated pyridine and picoline. The mechanism of the catalytic C-S bond cleavage of pyridine-2-thiol was proposed.

对双核铂（III）配合物的反应性和功能性的研究数量有限。为了阐明双核铂（III）配合物的反应活性，我们研究了5-甲基吡啶硫醇根桥联双核铂（III）配合物在5-甲基吡啶硫醇根桥联双核铂（III）配合物催化下与H_2的反应以及吡啶-2-硫醇的氢解反应。结果表明：（1）5-甲基吡啶硫醇根桥联双核Pt（III）配合物在150 ℃下与氢在DMF中反应时，桥联配体的C-S键发生断裂，生成3-甲基吡啶。释放的甲基吡啶的量随着施加的氢气压力的增加而增加。(2)研究了5-甲基吡啶硫醇桥联双核铂（III）配合物对吡啶-2-硫醇C-S键断裂的催化活性。Pt（III）配合物的催化活性高于相应的Pt（II）配合物。(3)Pt（III）配合物的催化活性取决于轴向配体的种类，其催化活性的大小顺序为Cl > Br > I。(4)吡啶硫醇在D_2气氛下氢解的^1H NMR研究表明，生成了氘代吡啶和甲基吡啶。提出了吡啶-2-硫醇催化C-S键断裂的机理。