4f轨道共性使单晶到单晶环开放异构化在Ce-IV-cyclopropenyl复合体中成为可能
Brett D Vincenzini1, Xiaojuan Yu2, Sébastien Paloc3
1Vagelos Laboratory for Energy Science and Technology, Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA.
Nature chemistry
|April 24, 2025
概括
这项研究揭示了复合体中显著的4f轨道共价性,推动了独特的反应性和环开放异构化. 这一发现促进了对f元素结合和化学转换的理解.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 固态化学 固态化学
背景情况:
- 在f元素化合物中,金属-合体的结合通常显示出高极化和最小的共价性质.
- 虽然5d/6d轨道以dative结合而闻名,但最近的研究表明4f/5f轨道参与金属-连接体结合.
- 4f轨道协同性和特定化学反应模式之间的直接联系需要进一步严格调查.
研究的目的:
- 为了研究4f轨道共性在f元素复合物的反应性中的作用.
- 探索一系列四价值MIV-cyclopropenyl复合体 (M = Ti,Zr,Ce,Hf,Th) 中的金属联体结合.
- 建立对d-和f-块金属复合体反应性的比较机械学的理解.
主要方法:
- 同结构MIV-cyclopropenyl复合物的合成和表征.
- 量子化学和光谱分析以探测金属-连接体结合.
- 单晶X射线衍射观察结构变化.
主要成果:
- 同源 (CeIV) 呈现出明显的4f-共价Ce=Cα相互作用.
- 这种共价相互作用会诱导环开环异体化反应在环烯基连接物中.
- 转变通过单晶到单晶的过程发生,保持结构完整性.
结论:
- 这项研究提供了令人信服的证据,证明4f-轨道共性影响化学反应.
- 这种共价性通过对比分析来证明,在d-和f-块金属复合体的同结构序列内.
- 这些发现为研究固态化学转换中的轨道共价效应开辟了新的途径.
更多相关视频
06:44From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
68.9K
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
相关概念视频
01:17Thermal Electrocyclic Reactions: Stereochemistry
1.9K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
1.9K
02:33Stereoisomerism of Cyclic Compounds
8.6K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
8.6K
03:26Electron Configuration of Multielectron Atoms
37.5K
The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
37.5K
02:52Stereoisomerism
11.6K
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...
11.6K
03:24Hybridization of Atomic Orbitals I
45.4K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
45.4K
02:42Valence Bond Theory
8.3K
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...
8.3K