一个四坐标Pr4+的伊米多素复合体
Andrew C Boggiano1, Sabyasachi Roy Chowdhury2, Michael D Roy1
1School of Chemistry & Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400, USA.
Angewandte Chemie (International ed. in English)
|July 16, 2024
概括
研究人员通过使用 imidophosphorane 配体合成了一种新的四价值普拉西奥迪复合物,[Pr4+(NPtBu3) 4. 这种独特的伪四面体复合体为兰坦化电子结构和晶体场效应提供了新的见解.
科学领域:
- 无机化学 无机化学
- 兰化物化学 兰化物化学
- 协调化学 协调化学
背景情况:
- 四价兰坦化物是罕见的,并且由于它们的高电荷密度而难以分离.
- 对于开发新材料和催化剂来说,了解类的电子结构至关重要.
- 伊米多酸配体具有独特的固体和电子特性,可以稳定不寻常的氧化状态.
研究的目的:
- 为了合成和表征一种新的四价值普拉西奥迪复合物.
- 为了研究四坐标Pr4+复合体的电子结构和磁性特性.
- 为了探索晶体场分裂和旋转轨道合在伪四面体兰坦化物之间的相互作用.
主要方法:
- 合成的四价普拉西奥迪复合物[Pr4+(NPtBu3) 4 .
- 使用单晶X射线衍射,电子磁共振 (EPR) 和L3边缘X射线近边缘光谱学 (XANES) 的表征.
- 磁感应度测量和多配置量子化学计算.
主要成果:
- 伪四面体四价普拉西奥迪复合物的隔离和结构阐明, [Pr4+(NPtBu3) 4].
- 展示了一种独特的电子结构,由于增加了晶体场效应,与异电子类型不同.
- 结晶场分裂和旋转轨道合的相互作用的实验和计算证据.
结论:
- 胺基酸连接体有助于稳定一种罕见的四价普拉西复合物.
- 伪四面体协调几何学显著影响Pr4+离子的电子和磁性.
- 这项研究提供了一种独特的分子模型,用于研究兰他尼德电子结构的基本方面.
相关概念视频
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
02:27Predicting Molecular Geometry
34.2K
VSEPR Theory for Determination of Electron Pair Geometries
34.2K
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
02:54Coordination Compounds and Nomenclature
21.3K
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...
21.3K
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
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
42.0K
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,...
42.0K