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Reactivity of the transition metal complexes containing azo, triazine, and hydrazone ligands

含有偶氮、三嗪和腙配体的过渡金属配合物的反应活性

基本信息

批准号：
15550048
负责人：
NAKAJIMA Kiyohiko
金额：
$ 1.22万
依托单位：
Aichi University of Education
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

This work initially arose from our research interest in the preparation of photo-and thermal-responsive metal complexes. Azoaromatic compounds are highly colored and have long been used as dyes and pigments. It is well known that the azo group is photoreactive and isomerizes between trans and cis conformers by irradiation of the π-π^* bands.We prepared new triazine ligands derived from 1-phenylazo-2-naphtylamine and pyridine-2-aldehyde or quinoline-2-aldehyde, and their palladium(II) complexes. The reversible ring opening and closure reactions of the coordinating dihydrotriazine ligand were observed by the addition of MeOH and (^nBu)_4NCl. The reaction can be understood in terms of competition between MeO^-and Cl^-ions.We, then, prepared hydrazone ligands derived from 2-hydrazinopyridine and 2-(alkylthio)benzaldehyde (R=Me,^tBu,4-chlorophenyl) or 2-(diphenylphosphino)beozaldehyde, and their metal complexes (M=Pd(II) and Pt(II). The NH hydrogen atoms of the coordinated hydrazone ligands were easily deprotonated, and protonated by the action of an acid. The reaction was followed spectrophotometrically, and the isosbestic points were observed. The uncoordinated hydrazone ligands and their palladium(II) complexes was not emissive, however, the platinum(II) complexes showed strong emission peaks in the visible region. Reversible large sifts of the emission peaks were observed by the action of acids and bases.

这项工作最初源于我们对制备光和热响应金属配合物的研究兴趣。偶氮芳香族化合物是高度着色的，长期以来一直被用作染料和颜料。众所周知，偶氮基团具有光反应性，并在π-π^*带的照射下在反式和顺式构象之间异构化。我们制备了由1-苯基偶氮-2-萘胺和吡啶-2-醛或喹啉-2-醛衍生的新的三嗪配体及其钯（II）配合物。通过MeOH和（^nBu）_4NCl的加入，观察了配位二氢三嗪配体的可逆开环和闭环反应。这个反应可以用MeO^和Cl^-离子之间的竞争来理解。然后，我们制备了由2-肼吡啶和2-（烷基硫代）苯甲醛（R=Me,^tBu，4-氯苯基）或2-（二苯基膦）苯甲醛及其金属配合物（M=Pd（II）和Pt(II)）衍生的腙配体。配位腙配体的NH氢原子容易去质子化，在酸的作用下也容易质子化。用分光光度法对反应进行跟踪，并对等吸点进行了观察。非配位腙配体及其钯（II）配合物不发射，而铂（II）配合物在可见光区有较强的发射峰。在酸和碱的作用下，观察到发射峰的可逆大筛。