1,3-二氨基-2-丙醇四乙酸双核锗(iv)-铥(iii)配合物的合成与结构

E. Martsinko, E. Chebanenko, I. Seifullina, V. Dyakonenko, S. Shishkina
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引用次数: 0

摘要

首次合成了新的杂核锗(IV)-铥(III)与1,3-二氨基-2-原聚四乙酸(h5 hpdta)配合物。配合物与配体的红外光谱对比分析表明,配合物的红外光谱中没有ν(СООН)吸收带,结构中不存在游离cooh基团。ν(С-N)吸收带(约45 cm -1)和ν(СН)吸收带(约5 cm -1)的显著位移以及ν(Ge-N)和ν(Tm-N)吸收带的存在证明质子化的氮原子与金属形成配位键。羧酸盐离子的两对ν as (СОО)和ν s (СОО)吸收带以及Ge-O和Tm-O键的伸缩振动证实了它们与金属的配位。配合物红外光谱中还存在ν as (Ge-O-Tm)、ν s (Ge-O-Tm)、δ (OH міст)和δ (Ge-OH)吸收带,说明配体的去质子化羟基与羟基的桥接性质以及锗在化合物结构中的水解形式。在90-150°С温度范围内的热分解过程中,由于吸热效应,两分子结晶水被移到气相中。在150-220°C左右,随着三个配位水分子的去除,可以看到进一步的内效应。在220 ~ 800°С温度范围内,配合物的氧化破坏伴随着三种外效应。在1000℃时最终热破坏的产物是geo2和tm2o3。根据配合物[Ge(ОН)(µ-hpdta)(µ-OH) Tm(h2o) 3]·2h2o的x射线衍射数据,德国的六配位原子和铥的八配位原子是由羟基和羟基阴离子的桥接氧原子结合的。Ge(1)原子的配位多面体是由去质子化羧基和羟基的3个O原子、hpdta5 -的氮原子和2个羟基阴离子的2个O原子组成的畸变八面体。铥的八配位原子的配位多面体是由去质子化羧基的1个O原子、去质子化的hpdta5 -羟基、羟基阴离子的桥接氧原子、配位水分子的3个O原子和hpdta5 -的1个n原子组成的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
SYNTHESIS AND STRUCTURE OF BINUCLEAR GERMANIUM(IV)-THULIUM(III) COMPLEX WITH 1,3-DIAMINO-2-PROPANOLTETRAACETIC ACID
New heteronuclear Germanium(IV)- Thulium (III) complex with 1,3-diamino-2-pro- panoltetraacetic acid (H 5 hpdta) was synthesized for the first time. Comparative analysis of IR-spectrum of complex and ligand proved the absence of free COOH-groups in the structure of compound – there are no ν(СООН) absorption bands in the IR-spectra of complex. The significant shift of the ν(С-N) absorption band (about 45 cm -1 ), ν(СН) (about 5 cm -1 ) and presence of ν(Ge-N) and ν(Tm-N) bands evidences that protonized nitrogen atoms form coordination bonds with metals. Two pairs of ν as (СОО) and ν s (СОО) absorption bands of carboxylate ions together with stretching vibrations of Ge-O and Tm-O bonds confirm their coordination to metals. There are also presented ν as (Ge-O-Tm), ν s (Ge-O-Tm), δ (OH міст ) and δ (Ge-OH) absorption bands in the IR-spectrum of complex that indicates the bridging nature of deprotonated hydroxy and hydroxyl group of ligand and also hydrolyzed form of germanium in the structure of compound. During thermal decomposition of the complex in the temperature range of 90-150 ° С as a result of the endothermic effect, two molecules of crystallization water are removed into the gas phase. The further endoeffects at around 150-220° C are seen with the removal of three coordinated water molecules. The oxidative destruction of the complexes is accompanied by the three exoeffects in temperature range 220-800 ° С. The products of final thermal destruction at 1000°C are GeO 2 and Tm 2 O 3 . According to the X-Ray diffraction data of complex [Ge(ОН)( µ -hpdta)( µ -OH) Tm(H 2 O) 3 ] ⋅ 2H 2 O, the six-coordinated atom of Germany and octa-coordinated atom of Thulium are bound by the bridging oxygen atom of hydroxyl group and hydroxyl-anion. The coordination polyhedron of Ge(1) atom is a distorted octahedron formed by three O atoms of deprotonated carboxyl and hydroxyl groups, the nitrogen atom of the hpdta 5– and two O atoms of two hydroxyl-anions. The coordination polyhedron of octa-coordinated atom of Thulium is formed by of the O atoms of deprotonated carboxyl, deprotonated hydroxyl groups of the hpdta 5– , the bridging oxygen atom of hydroxyl-anion, three O atoms of coordinated water molecules and one N-atom of the hpdta 5– .
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