检查对的电子结构的连接物变化的影响
John J Kiernicki1, Maryline G Ferrier2, Juan S Lezama Pacheco3
1H.C. Brown Laboratory, Department of Chemistry, Purdue University , West Lafayette, Indiana 47907, United States.
Journal of the American Chemical Society
|October 13, 2016
概括
高度减少的 (IV) 复合物激活了阿里拉和,形成了跨 (bis) 型物种. 结合物修饰和氧化揭示了不同的氧化状态和电子结构,通过光谱学和晶体学得到证实.
科学领域:
- 有机金属化学
- 化学
- 连接物设计
背景情况:
- 具有氧化还原活性联体的复合物具有独特的反应性.
- 在催化和合成中,激活含的小分子至关重要.
研究的目的:
- 通过减少的 (IV) 复合物对化物和原体的激活进行研究.
- 探索产生的物种的电子结构和氧化状态.
- 描述新型的 - 胺复合物.
主要方法:
- 合成 (IV) 复合物与 (二胺) 连接物.
- 与阿里拉齐德和迪亚根的反应.
- 频谱表征 (NMR,UV-Vis,XAS) 的方法
- 进行X射线结晶学.
主要成果:
- (IV) 复合物很容易将亚里拉化物降解为 (V) 类型.
- 迪亚裂变对特定的复合物具有选择性.
- 连接物修饰和氧化导致具有不同的电子结构的 (V) 和 (VI) 种.
- 离子 (VI) 复合物被分离和表征.
结论:
- 在复合物中,具有氧化活性的二胺配体能够产生多种反应性.
- 三联体促进N3R和N=N键的减少.
- 通过配体设计和氧化来调整复合物的电子特性是可以实现的.
相关概念视频
Metal-Ligand Bonds
25.3K
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...
25.3K
Crystal Field Theory - Octahedral Complexes
31.5K
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...
31.5K
Valence Bond Theory
11.5K
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...
11.5K
Complexometric Titration: Ligands
2.5K
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...
2.5K
Structural Isomerism
22.4K
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...
22.4K
Colors and Magnetism
14.4K
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...
14.4K


