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具有“夹钳”配体 2,6-[O(CH2CH2)2NCH2]2C6H3--的有机汞(II)和碲(II)化合物--稳定一种不寻常的有机碲(II)阳离子物种。

Organomercury(II) and tellurium(II) compounds with the "pincer" ligand 2,6-[O(CH2CH2)2NCH2]2C6H3--stabilization of an unusual organotellurium(II) cationic species.

机构信息

Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-Bolyai, RO-400028, Cluj-Napoca, Romania.

出版信息

Dalton Trans. 2011 Sep 21;40(35):8830-8. doi: 10.1039/c1dt10414d. Epub 2011 Jul 11.

DOI:10.1039/c1dt10414d
PMID:21743935
Abstract

The reaction of RH (1) with Hg(OAc)(2), in EtOH, gave the acetate RHgOAc (2) [R = 2,6-O(CH(2)CH(2))(2)NCH(2)C(6)H(3)]. The corresponding RHgCl (3) was obtained from 2 and LiCl. The reaction of 3 with TeCl(4) (1:1 molar ratio), in anhydrous 1,4-dioxane, resulted in the transfer of the organic ligand from mercury to tellurium and the isolation of the unexpected ionic compounds RTe[Hg(2)Cl(6)] (4) and [RH(3)][HgCl(4)] (5). The molecular structures of 1-4 and 5·H(2)O were established by single-crystal X-ray diffraction. The acetate 2 and the chloride 3 are monomeric in solid state. In both mercury and tellurium organometallic compounds the organic group acts as an (N,C,N) "pincer" ligand. This coordination pattern provided stability for the rare RTe cation. Weak cation-anion interactions [Te···Cl 3.869(3) Å] are present between RTe and the dinuclear anion Hg(2)Cl(6) in the crystal of 4. Theoretical calculations with DFT methods were performed for models of 3 and 4. The results show that in the cation of 4 the coordination of the nitrogen atoms play an important role for the stabilization of the structure found in the crystal whereas in 3 the coordination of the nitrogen atoms to the metal centre stabilizes to a less extent the structure found in solid state.

摘要

RH(1)与 Hg(OAc)(2)在乙醇中的反应生成了醋酸盐 RHgOAc(2)[R=2,6-O(CH(2)CH(2))(2)NCH(2)C(6)H(3)]。相应的 RHgCl(3)可由 2 和 LiCl 制得。3 与 TeCl(4)(1:1 摩尔比)在无水 1,4-二氧六环中的反应导致有机配体从汞转移到碲,并分离出意想不到的离子化合物RTe[Hg(2)Cl(6)](4)和[RH(3)][HgCl(4)](5)。通过单晶 X 射线衍射确定了 1-4 和 5·H(2)O 的分子结构。在固态中,醋酸盐 2 和氯化物 3 均为单体。在汞和碲有机金属化合物中,有机基团充当(N,C,N)“钳”配体。这种配位模式为罕见的RTe阳离子提供了稳定性。在 4 的晶体中,存在弱的阴阳离子相互作用[Te···Cl 3.869(3)Å],其中RTe与双核阴离子Hg(2)Cl(6)之间存在弱的阴阳离子相互作用。用 DFT 方法对 3 和 4 的模型进行了理论计算。结果表明,在 4 的阳离子中,氮原子的配位对晶体中发现的结构的稳定起着重要作用,而在 3 中,氮原子与金属中心的配位对在固态中发现的结构的稳定作用较小。

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