Abstract

The reactions of functionalized lithium CF₃-β-diketonate (LiL) with trivalent rare-earth metal salts in methanol afford homobinuclear and heterobi(tri)nuclear complexes depending on the nature of the transition metal and anion (chlorides, nitrates, and acetates). In the cases of lanthanum(III) and cerium(III), homoleptic complexes [(LnL₃)₂] are isolated (CIF files CCDC nos. 2031097 (Ia) and 2031102 (Ib)). The reaction of LiL with praseodymium(III) nitrate gives the new trimetallic structure [(LiPrL₃)(LiL)(NO₃)(H₂O)₂] (CIF file CCDC no. 2031103 (II)), and the replacement of nitrate by chloride gives [(PrL₃)(LiL)(H₂O)] (CIF file CCDC no. 2031104 (IIIa)). Regardless of the nature of the anion of the salt in the series from neodymium(III) to ytterbium(III) and yttrium(III), Ln–Li β-diketonates [(LnL₃)(LiL)(solv)] (solv is H₂O and MeOH) are formed, and their structures are characterized by X-ray structure analysis (CIF files CCDC nos. 2031099 (IIIb), 2031100 (IIIc), 2031098 (IVa), 2031096 (IVc), 2031094 (IVf), 2031101 (IVg), and 2031095 (IVh)). The equilibrium of the diketonate isomeric forms in a solution of deuterated dimethyl sulfoxide is studied by ¹⁹F NMR spectroscopy, and the qualitative composition of the polynuclear complexes is determined by mass spectrometry.

中文翻译：

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含稀土金属同核和异核配合物合成中的功能化含三氟甲基β-二酮酸锂

摘要

根据过渡金属和阴离子的性质（氯化物，硝酸盐和乙酸盐），官能化的CF ₃ -β-二酮酸锂（LiL）与三价稀土金属盐在甲醇中的反应可得到同核和杂双（三）核配合物。在镧（III）和铈（III）的情况下，分离出均纯复合物[（LnL ₃）₂ ]（CIF文件CCDC号2031097（I a）和2031102（I b））。LiL与硝酸ody（III）的反应产生了新的三金属结构[（LiPrL ₃）（LiL）（NO ₃）（H ₂ O）₂ ]（CIF文件CCDC编号2031103（II）），然后用氯化物代替硝酸盐得到[（PrL ₃）（LiL）（H ₂ O）]（CIF文件，CCDC号2031104（III a））。无论从钕（III）到（III）和钇（III）系列中盐的阴离子的性质如何，Ln-Liβ-二酮酸酯[（LnL ₃）（LiL）（solv）]（solv is形成H ₂ O和MeOH），并通过X射线结构分析对其特征进行表征（CIF文件CCDC号2031099（III b），2031100（III c），2031098（IV a），2031096（IV c）， 2031094（IV f），2031101（IV g）和2031095（IV h））。通过¹⁹ F NMR光谱研究了氘代二甲基亚砜溶液中二酮酸酯异构体形式的平衡，并通过质谱法确定了多核配合物的定性组成。