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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterization of gold(III) complexes possessing 2,9-dialkylphenanthroline ligands: to bind or not to bind?
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Synthesis and characterization of gold(III) complexes possessing 2,9-dialkylphenanthroline ligands: to bind or not to bind?

机译：具有2,9-二烷基菲咯啉配体的金（III）配合物的合成与表征：要结合还是不结合？

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In an effort to discover potential alternatives to the anti-cancer drug cisplatin, the synthesis of gold(III) polypyridyl coordination complexes was pursued. Specifically, this report describes the synthesis and characterization of a series of 2,9-dialkyl-1,10-phenanthroline ((R)phen) gold(III) coordination complexes (R = n-butyl, sec-butyl, and tert-butyl). Due to the steric hindrance imparted by the alkyl substituents, these ligands do not react with HAuCl4 to form square-planar gold(III) dichloride complex ions, as is the case with 1,10-phenanthroline, but instead form salts comprised of [AuCl4](-) anions and protonated 2,9-dialkylphenanthroline cations (compounds 1 and 2). In an effort to facilitate direct binding between the substituted phenanthroline and the gold(III) metal center, reactions were carried out between the ligand and NaAuCl4 in the presence of a Ag(I) salt. The precipitation of one equivalent of AgCl afforded the formation of neutral, distorted square-pyramidal gold( III) trichloride complexes (compounds 3 and 4). Primary or secondary substitutions at the alpha carbon of the alkyl substituent allow direct metal-ligand coordination, whereas a tertiary substituent inhibits chelation and results only in the formation of a salt comprised of a protonated phenanthroline cation and a [AuCl2]- anion (compound 5). Compounds 1-4 have been characterized by H-1 NMR, UV/vis, IR spectroscopy, and X-ray crystallography.
机译：为了发现抗癌药物顺铂的潜在替代品，金（III）聚吡啶基配位化合物的合成一直在进行。具体而言，该报告描述了一系列2,9-二烷基-1,10-菲咯啉（（R）phen）金（III）配位化合物（R =正丁基，仲丁基和叔丁基丁基）。由于烷基取代基所赋予的位阻，这些配体不会与HAuCl4反应形成正方形平面的二氯化金（III）络合物离子，就像1,10-菲咯啉的情况一样，而是形成由[AuCl4 ]（-）阴离子和质子化的2,9-二烷基菲咯啉阳离子（化合物1和2）。为了促进取代的菲咯啉和金（III）金属中心之间的直接结合，在Ag（I）盐存在下在配体和NaAuCl 4之间进行反应。一当量的AgCl的沉淀提供了中性的，扭曲的方形-金字塔形的三氯化金（III）配合物（化合物3和4）的形成。烷基取代基的α碳上的伯或仲取代可实现直接的金属-配体配位，而叔取代基可抑制螯合，仅导致形成由质子化菲咯啉阳离子和[AuCl2]-阴离子组成的盐（化合物5 ）。化合物1-4已经通过H-1 NMR，UV / vis，IR光谱和X射线晶体学表征。

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