一个与核友性艾伦利丁连接体的动因组合物
Osvaldo Ordoñez1, Xiaojuan Yu2, Megan A Schuerlein1
1Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106, United States.
Journal of the American Chemical Society
|October 7, 2024
概括
复合物经历环环开放以形成烯复合物. 这些复合物与电友反应并经历二元化,DFT计算显示了电子移位和旋转轨道效应.
科学领域:
- 有机金属化学
- 化学
- 连接体设计
背景情况:
- 环烯基化合物是紧张的三环.
- 有机金属由于可访问的f轨道而具有独特的反应性.
- 在有机金属合成中,艾伦利丁连接物是多功能构建块.
研究的目的:
- 为了研究环复合物的反应性.
- 合成和描述新的乙烯复合物.
- 使用DFT探索这些复合物的电子结构和结合.
主要方法:
- [Cp3Th(3,3-二cyclopropenyl) 与二胺 (LDA) 的反应
- 乙烯复合物及其衍生物的分离和表征.
- 用于电子结构分析的密度功能理论 (DFT) 计算.
主要成果:
- [Cp3Th(3,3-二cyclopropenyl) 的环开口与LDA产生烯复合物[Li(Et2O) 2][Cp3Th(CCCPh2) ([1]).
- 复合物 [1] 经过二元化形成[Cp2Th(μ:η1:η3-CCCPh2) ]2 (2) 并与MeI和相反应,分别产生乙和四乙.
- DFT计算证实了利丁联体中显著的电子移位,并与实验性13C NMR移位一致,表明来自Th 5f轨道的旋转轨道效应.
结论:
- 环烯复合物可以有效地转化为乙烯复合物.
- 乙烯联体对电友具有丰富的反应性,并经历二元化.
- DFT研究为这些新型复合物的电子结构和结合提供了宝贵的见解.
相关概念视频
Metal-Ligand Bonds
20.6K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.6K
Complexation Equilibria: The Chelate Effect
472
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
472
Valence 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
Complexometric Titration: Ligands
921
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
921
Complexation Equilibria: Factors Influencing Stability of Complexes
347
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
347
Crystal Field Theory - Octahedral Complexes
26.2K
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...
26.2K


