非古典与古典金属...H3C-C相互作用:通过中子衍射,数据库分析,溶液动力学和DFT研究来准确地描述14电子的鲁丁系统,数据库分析,溶液动力学和DFT研究
Walter Baratta1, Carlo Mealli, Eberhardt Herdtweck
1Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine, Via Cotonificio 108, I-33100 Udine, Italy. inorg@dstc.uniud.it
Journal of the American Chemical Society
|April 29, 2004
概括
这项研究使用中子衍射定义了复合体中的三角离子相互作用. 它揭示了这些相互作用和甲基组扭曲之间的相关性,涵盖了古典到非古典类型.
科学领域:
- 有机金属化学 有机金属化学
- 固态化学 固态化学
背景情况:
- 在有机金属化学中,对抗性相互作用至关重要,它会影响反应性和稳定性.
- 了解这些相互作用需要精确的结构和电子表征.
研究的目的:
- 通过中子衍射精确地定义一个复合体中的三角形气体相互作用.
- 为了研究吸毒相互作用和甲基组扭曲之间的关系.
- 探索溶液中基替代剂的动态行为.
主要方法:
- 在RuCl的结构分析中使用中子衍射(2)[PPh(2)(2,6-Me(2)C(6)H(3)) ](2).
- 相关复合体的X射线结构调查.
- 1H NMR线形状分析以确定激活参数.
- 密度函数理论 (DFT) 优化和分子轨道 (MO) 分析.
主要成果:
- 定义了与特定的Ru...C和Ru...H距离的三角形杂态相互作用.
- 建立了MC-C角度和甲基组扭曲之间的线性相关性.
- 观察到溶液中的分子内重新排列,平衡正向CH3) 组.
- DFT计算支持实验发现,识别了杂态相互作用的过渡状态.
结论:
- 在这个系统中,对抗性相互作用的范围从经典 (M...meta(2) -HC) 到非经典 (M...meta(3) -H(2) C) 类型.
- 溶液中的动态过程受到替代物的固体体积的影响.
- 计算方法可以准确地模拟气体相互作用和旋转障碍.
更多相关视频
07:54Analysis of AtHIRD11 Intrinsic Disorder and Binding Towards Metal Ions by Capillary Gel Electrophoresis and Affinity Capillary Electrophoresis
Published on: August 22, 2018
06:53Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
相关概念视频
02:37Metallic Solids
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...
02:42Valence Bond Theory
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...
02:58Crystal Field Theory - Octahedral Complexes
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...
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
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,...
01:07Ladder Diagrams: Complexation Equilibria
Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
01:28Ionic Association
The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.