Synthesis of polynuclear hetero-metal complexes of Bi-p, -d, and -f block elements

Bi-p、-d 和 -f 嵌段元素多核异金属配合物的合成

• 批准号: 12640543
• 负责人: ASATO Eiji
• 金额: $ 2.3万
• 依托单位: University of the Ryukyus
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640543/
• 关键词: Polynuclear hetero-metal comnlex; Bismuth complex; Polymetallic oxide; X-ray crystal structure analysis; Powder X-ray diffraction; Thermal decomposition; Cluster comniex; ビスマス錯体; 異種金属二核錯体; 錯体分解法; X線構造解析; 異種金属多核錯体; 金属酸化物

In order to establish rational preparative method to create Bi-based hetero-metal dinuclear complexes, a new phenol-based ligand H_6L was prepared. Reaction of H_6L with Bi(N0_3)_3・5H_2O afforded mononuclear Bi complex [Bi(H_3L)]・H_2O, where Bi atom is trapped into "Bi-recognition site" embedded in the ligand.This complex still contains an empty coordination site for a second metal ion, and indeed reacts with a variety of d-block and p-block elements.Successfully isolated dinuclear complexes are as follows ; Bi-V(IV)=O, -Cr(III), -Mn(III), -Fe(III), -Co(llI), -Ni(II), -Cu(II), -Zn(II), and -AI(III).As potential precursors for polymetallic oxides, thermal decomposition process of these complexes was examined using TGA analysis and XRD measurement.As a representative case, Bi-Cu hetero-nuclear complex loses all of its organic ingredients at around 300℃ to become a mixture of Bi_2CuO_4, Bi_2O_3, and CuO.The latter two ingredients further react each other at higher temperatures, and finall … More y causing disappearance of Bi_2O_3 ingredient above 600℃.Another approach to hetero-metal clusters was also examined.A commercially available ligand N-2-hydroxyethyl)iminodiacetic acid(H_3heida)reacts with Bi ion in a mixed solvent of aqueous ammonia and methanol to give trinuclear Bi complex (NH_4)[Bi_3(heida)_3(OH)]・6H_2O・MeOH.Its structure is characterized as an incomplete cuban[Bi_3(μ-O_<alkoxo>alkoxo)_3(μ_3-OH)], where the three Bi atoms are bridged by the hydroxide ion (μ_3-OH) and adjacent Bi pairs are further bridged by the alkoxo oxygen of heida^<3->.The metal deficient position of the pre-cubane is occupied by NH^+_4 through hydrogen bonding toward the three bridging alkoxo oxygens.The NH^+_4 can be easily replaced by K^+ to form a mixed cluster [Bi_3K(μ_3-O)_4].This finding suggests that the trinuclear pre-cubane may function as a potential precursor for the mixed clusters of [Bi_3M(μ_3-O)_4] type, where M is d-block and p-block elements, while no such mixed metal clusters have been obtained yet. Less

为了建立合理的制备方法来制备铋基异金属双核配合物，合成了一种新的苯酚基配体H6L。H_6L与Bi(NO_3)_3·5H_2O反应生成了单核铋配合物[Bi(H_3L)]·H_2O，其中铋原子被束缚在配体中的“铋识别位”中。该络合物仍含有一个空的第二金属离子配位，并确实与多种d-嵌段和p-嵌段元素发生反应。BiV(IV)=O，-Cr(III)，-Mn(III)，-Fe(III)，-Co(LLi)，-Ni(II)，-Cu(II)，-Zn(II)和-Al(III)。作为多金属氧化物的潜在前驱体，用热重分析和X射线衍射仪研究了这些配合物的热分解过程。作为一个典型的例子，在300℃左右，铋铜异核配合物失去了所有的有机成分，形成了Bi2CuO4，Bi2O3，Bi2CuO4和Bi2O3的混合物，和…。后两种成分在更高的温度下进一步相互反应，最终形成CuO另一种形成异金属簇合物的途径是：在氨水和甲醇的混合溶剂中，N-羟乙基亚氨基二乙酸(H_3HEIDA)与铋离子反应生成三核铋配合物(NH_4)[Bi3(Heida)_3(OH)]·6H_2O·MeOH，其结构为不完全的古巴[Bi3(μ-O&lt；烷氧基-GT；烷氧基)_3(μ_3-OH)]，其中三个铋原子通过氢氧离子(μ_3-OH)桥联，相邻的铋对进一步通过Heida^&lt；3-&gt的烷氧基氧桥联；[Bi3M(μ_3-O)_4]型[Bi3M(μ_3-O)_4]型前立方烷可能是一种潜在的前驱体，其中M是d-嵌段元素和p-嵌段元素。较少