获得同质中性和阴离子五坐标 Pr ((iv) 氧化复合物
Pragati Pandey1, Megan Keener1, Thayalan Rajeshkumar2
1Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL) CH-1015 Lausanne Switzerland marinella.mazzanti@epfl.ch.
Chemical science
|October 15, 2025
概括
新的反应条件使得稳定的四价普拉西 (Pr(iv)) 复合物的合成成为可能. 这项研究详细介绍了新型Pr(iv) 氧化复合物的分离和表征,扩大了这种具有挑战性的氧化状态的已知例子.
科学领域:
- 无机化学 无机化学 有机化学
- 有机金属化学 有机金属化学
- 材料科学 材料科学 材料科学
背景情况:
- 结构性特征的四价普拉西奥迪 (Pr(iv)) 复合物是罕见的,因为难以稳定这种氧化状态.
- 现有的研究只确定了有限数量的Pr ((iv) 例,突出了需要新的合成策略和稳定连接体的需要.
- 开发方法,以获得更高的氧化状态在兰坦化物是探索其独特的电子和磁性质的关键.
研究的目的:
- 确定特定的反应条件和试剂,以促进先前难以捉摸的Pr(iv) 复合物的合成和分离.
- 为了合成和充分描述使用三-丁) 氧化和三-氧化连接体的新型Pr (iv) 复合物.
- 研究氧化剂和溶剂等反应参数对高价值Pr (iv) 物种的稳定性和隔离性的影响.
主要方法:
- 氧化前体praseodymium ((iii) 复合物,使用二氨基基离子四二甲酸 (thiaBF4) 氧化剂.
- 分离并完全描述由此产生的Pr(iv) 复合物,包括[Pr(OSi(OtBu)3)4] (2-PrOtBu) 和[MPr(OSiPh3)5] (5M-PrPh) (M = K, Cs).
- 固态结构分析,电化学研究,理论计算,电子磁共振 (EPR) 和SQUID磁力测量用于表征.
主要成果:
- 成功合成和分离了四种新的Pr(iv) 复合物,包括第一个离子兰坦化物(iv) 复合物的例子 ([MPr(OSiPh3) 5和[KDB18C6][Pr(OSiPh3) 5).
- 证明特定的试剂 (thiaBF4超过魔幻蓝) 和非协调溶剂对于稳定Pr是至关重要的.
- 通过光谱,磁性,结构和电化学技术的结合来确认Pr (iv) 的氧化状态.
结论:
- 该研究成功地为合成稳定的Pr(iv) 复合物建立了新的反应条件,显著扩大了已知的例子的范围.
- 阳离子Pr(iv) 复合物的发展为调整氧还原潜力和获得更稳定的高价值类物种提供了新的途径.
- 这项工作为进一步探索高价值化物化学及其潜在应用提供了基础.
相关概念视频
02:42Valence Bond Theory
11.2K
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...
11.2K
02:34Structural Isomerism
21.5K
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...
21.5K
02:54Coordination Compounds and Nomenclature
26.3K
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
26.3K
02:52Stereoisomerism
13.9K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
13.9K
02:57Coordination Number and Geometry
18.9K
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.
18.9K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
48.1K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
48.1K