平面四度,六度,八度和十度坐标较重的土金属:d轨道与碳链的共价相互作用
Xin-Bo Liu1, Yi-Fan Yang1, Li-Juan Cui1
1Institute of Atomic and Molecular Physics, Jilin University, Changchun 130023, China. zcui@jlu.edu.cn.
Physical chemistry chemical physics : PCCP
|August 29, 2025
概括
较重的土金属形成具有碳链的独特平面超协调物种. 它们的d轨道和大尺寸使得新型的结合能够形成稳定,低协调的结构.
科学领域:
- 无机化学
- 计算化学
- 材料科学
背景情况:
- 较重的土金属 (Ae=Ca,Sr,Ba) 具有较大的原子半径和可访问的d轨道,扩大了平面协调化学的可能性.
- 获得这些金属的低协调类型具有重大合成挑战.
- 平面高坐标物种 (phAe) 代表了理解结合和结构的前沿.
研究的目的:
- 研究中性土金属碳链 (AeCn) 复合物的潜在能量表面 (n = 4-12).
- 确定稳定的平面高协调土金属物种及其协调几何形状.
- 阐明这些新型结构形成的电子和粘合特性.
主要方法:
- 对AECn复合体的潜在能量表面的计算探索.
- 最低能量的配置及其几何对称性的分析.
- 研究电荷转移和轨道相互作用 (d-轨道,σ-移位键).
主要成果:
- 具有n=4,6,8和BaC10的AeCn复合体表现出最低的能量,具有C2v对称的平面四,六,八和十坐标几何.
- 曲的碳链部分封装了平面高坐标的土金属中心.
- 奇数AeCn复合体表现为较不稳定的局部最小值或扭曲的结构.
- 电荷转移到偶数的碳链诱导多态性质,增强静电相互作用.
- 涉及AEd轨道和σ碳键的显著共价相互作用有助于热力学稳定性.
结论:
- 较重的土金属的d轨道在稳定独特的平面超坐标结合图案中起着至关重要的作用.
- 由于有利的电子相互作用,偶数的碳链有利于形成稳定的phAe复合体.
- 这项研究提供了前所未有的低坐标金属碳结构的形成和稳定性的基本见解.
相关概念视频
02:42Valence Bond Theory
9.2K
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...
9.2K
03:51Molecular Orbital Theory II
19.6K
Molecular Orbital Energy Diagrams
19.6K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
44.2K
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,...
44.2K
02:58Crystal Field Theory - Octahedral Complexes
27.4K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
27.4K
02:40MO Theory and Covalent Bonding
11.2K
The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
11.2K
03:35Hybridization of Atomic Orbitals II
33.7K
sp3d and sp3d 2 Hybridization
33.7K