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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >~1H-NMR studies on the ternary complexes of rare-earth ions with thenoyltrifluoroacetone and polyethers in dichloromethane
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~1H-NMR studies on the ternary complexes of rare-earth ions with thenoyltrifluoroacetone and polyethers in dichloromethane

机译：〜1H-NMR研究二氯甲烷中稀土离子与壬基三氟丙酮和聚醚的三元络合物

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摘要

The structures of the ternary complexes of lanthanoid and yttrium (Ln3+)–thenoyltrifluoroacetonates (tta-) with polyether (POE) in organic phase were investigated by 1H-NMR spectroscopy, where the POEs are crown ethers (18-crown-6 and benzo-18-crown-6) and monodispersed linear polyethers (DEOn: HO–(CH2CH2O–)nC12H25, where n = 4, 6, 8). The changes in chemical shift of methylene protons of POE by addition of the adduct complex [Ln(tta)3(POE)] were measured at various Ln3+-to-POE concentration ratios. Chemical shift changes for each proton of POE by the formation of [Ln(tta)3(POE)] were determined. Results revealed that oxygen atoms at the hydroxyl terminal of linear POE have higher tendency to coordinate to the metal ion in [Ln(tta)3] complex. Three (for La3+) or two (for Lu3+ or Y3+) oxygen atoms of the POE coordinate to the metal ion without substitution of ttaligands to satisfy the metal ion’s coordination number of nine or eight, respectively. In the case of 18-membered crown ether complexes, La3+ is incorporated inside the cavity of the POE, displacing one of the three tta- from the inner coordination sphere while the other two remain coordinated to the metal ion. On the other hand, for the adduct of Y3+ complex with crown ether, all three tta- ligands are directly coordinating to the metal ion.
机译：通过1H-NMR光谱研究了镧系元素和钇（Ln3 +）-壬基三氟丙酮酸（tta-）与聚醚（POE）在有机相中的三元复合物的结构，其中POE为冠醚（18-crown-6和苯并- 18-crown-6）和单分散线性聚醚（DEOn：HO–（CH2CH2O–）nC12H25，其中n = 4、6、8）。在不同的Ln3 + -POE浓度比下，通过添加加合物[Ln（tta）3（POE）]测量了POE的亚甲基质子的化学位移变化。通过[Ln（tta）3（POE）]的形成，确定每个POE质子的化学位移变化。结果显示，线性POE羟基末端的氧原子具有更高的配位到[Ln（tta）3]络合物中的金属离子的趋势。 POE的三个（对于La3 +）或两个（对于Lu3 +或Y3 +）氧原子与金属离子配位而不取代链配体来分别满足金属离子的配位数9或8。在18元冠醚络合物的情况下，La3 +被掺入POE的腔体内，使三个ta-中的一个从内部配位球中移出，而另外两个则与金属离子保持配位。另一方面，对于Y3 +络合物与冠醚的加合物，所有三个tta-配体均直接与金属离子配位。

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