聚氧甲酸连接体揭示了兰化物和重型动因化物之间不同的协调化学物质
Ian Colliard1,2, Gauthier J-P Deblonde1,3
1Physical and Life Sciences Directorate, Glenn T. Seaborg Institute, Lawrence Livermore National Laboratory, Livermore, California 94550, United States.
JACS Au
|July 26, 2024
概括
研究人员开发了一种新方法,仅使用微克物质来合成乙化物和化物协调化合物. 这一突破允许对f块元素化学进行有效研究,揭示了4f和5f元素之间的根本差异.
科学领域:
- 无机化学 无机化学
- 协调化学 协调化学
- 放射化学 放射化学是指辐射化学.
背景情况:
- 试验性研究的行为化合物受到放射性,稀缺性和同位素的成本的限制.
- 由于数据不足,对f块金属,特别是转石乙烯化物,协调化学的理解落后于其他元素.
- 转石乙化物经常被事地认为与三价兰坦化物相似,但实验证据很少.
研究的目的:
- 开发一种高效的合成方法,以在相同的条件下生产兰坦化物和重型活性化物协调化合物.
- 建立一个一致的平台来比较f块元素的协调化学.
- 在相同的协调环境中,研究兰坦化物 (4f) 和活性化物 (5f) 之间的基本化学差异.
主要方法:
- 三价f元素的合成复合到多氧甲酸盐 (POM) 配体PW11O397-.
- 十七个单晶X射线衍射 (XRD) 结构的表征,包括完整的兰坦化物系列,伊,奇和美洲.
- 采用了1:2的金属:配体比,为所有研究的f元素产生了8个协调的正方形反 prismatic 复合体.
主要成果:
- 成功合成和结构性表征了一系列兰化物和重活性化物POM化合物,包括前两个Am3+-POM和一个Cm-POM化合物.
- 合成化合物的所有f元素都表现出8坐标,方形反 prismatic 几何,提供了一个一致的结构框架.
- 观察到早期和晚期的兰坦化物,兰坦化物和动态化物之间的显著晶体和光谱差异,甚至在美洲和奇之间,尽管有相似的协调球.
结论:
- 开发的金属结合体系统使f元素协调化合物的高效合成能够使用最小的材料.
- 该研究提供了一个多功能平台,用于放大和观察f块元素中的微妙差异.
- 4f和5f元素之间存在着根本性的化学差异,即使在相同的协调环境中,它们也不能仅仅归因于大小.
更多相关视频
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
6.4K
09:38Fabrication Procedures and Birefringence Measurements for Designing Magnetically Responsive Lanthanide Ion Chelating Phospholipid Assemblies
Published on: January 3, 2018
7.2K
相关概念视频
02:51Metal-Ligand Bonds
20.7K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.7K
00:43Complexometric Titration: Ligands
939
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
939
02:42Valence Bond Theory
8.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.5K
02:57Coordination Number and Geometry
15.7K
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
15.7K
02:34Structural Isomerism
19.2K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.2K
03:02Colors and Magnetism
11.6K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.6K