基桥式二铜复合物的电子结构和反应性
Kurtis M Carsch1, James T Lukens2, Ida M DiMucci2
1Department of Chemistry and Chemical Biology , Harvard University , 12 Oxford Street , Cambridge , Massachusetts 02138 , United States.
Journal of the American Chemical Society
|January 10, 2020
概括
合成和减少了双铜复合物与帕克曼二林配体. 由此产生的伊米德复合物表现出NAr局部自旋,使得像C-H氨基化一样的激素促进反应.
科学领域:
- 协调化学
- 有机金属化学
- 催化剂
背景情况:
- 双核,帕克曼二氧化联体支架对于模拟双铜复合体是有效的.
- 中性伊米德复合物 (Rdmx) Cu2 ((μ2-NAr) 的合成涉及二基前体和亚利基.
研究的目的:
- 合成和描述新的二铜胺复合物.
- 研究减少的二铜伊米德和伊米尼尔复合物的电子结构和反应性.
- 探索激素促进的反应性,包括C-H氨基化,转移和H原子抽象.
主要方法:
- 通过去质子化/金属化或转金属化合成二铜复合物.
- 使用石墨或其他化学减少剂来减少伊米德复合物.
- 包括EPR,X射线吸收 (Cu L2,3/K边缘,N K边缘) 和光学光谱的光谱表征.
- 使用DFT/CASSCF计算进行计算分析.
主要成果:
- 成功合成了中性化物复合物 (Rdmx) Cu2 ((μ2-NAr).
- 一个特定复合体的单电子还原启动了分子内基C-H氨化.
- 化学还原产生可分离的伊米尼尔复合物[{Rdmx) Cu2{μ2-NAr) ]−.
- 减少的复合物是正式的IIIA类混合价值体,具有显著的NAr局部自旋.
- 反应性受到基替代剂的影响,影响N基性质.
结论:
- 减少的二铜胺复合体具有独特的电子结构和反应性.
- 减少复合体中的NAr局部自旋促进了基因促进的转化.
- 在调整这些复合物的N基性质和反应性方面,基替代剂起着至关重要的作用.
更多相关视频
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
12.6K
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
10.1K
相关概念视频
02:42Valence Bond Theory
10.9K
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...
10.9K
02:57Coordination Number and Geometry
18.6K
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
18.6K
03:02Colors and Magnetism
13.7K
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...
13.7K
02:51Metal-Ligand Bonds
23.6K
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...
23.6K
02:34Structural Isomerism
21.4K
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...
21.4K
02:58Crystal Field Theory - Octahedral Complexes
30.2K
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...
30.2K