在三坐标 (I) 碳复合体中旋转异构体和连接体异构化
Malik H Al-Afyouni1, Elizaveta Suturina2,3, Shubhrodeep Pathak2
1Department of Chemistry, University of Rochester , Rochester, New York 14618, United States.
Journal of the American Chemical Society
|August 13, 2015
概括
这项研究揭示了复合物在旋转状态和结构之间迅速切换. 这种半联体行为为过渡金属催化和旋转动力学提供了新的见解.
科学领域:
- 有机金属化学
- 催化剂
- 旋转交叉
背景情况:
- 在过渡金属催化过程中,基连接体对于创建可访问的协调位点至关重要.
- 连接物可变性会影响金属中心的电子性质,包括自旋状态.
- 了解旋转状态的变化是控制催化活性和反应途径的关键.
研究的目的:
- 为了研究一种表现出可溶性和快速旋转状态的I系统.
- 描述一种具有异常二基酸结合模式的新型 (I) 单碳复合物.
- 阐明旋转同位素相互转换的机制和热力学.
主要方法:
- 合成和表征 (I) 单碳酸复合物L (tBu) Co (CO).
- 溶液光谱 (NMR,电子吸收) 用于研究旋转异构体群和动态.
- 计算模型 (最小能量交叉点计算) 来确定反应路径.
主要成果:
- 复合物存在于固体状态,但在溶液中存在一个显著的三元体群.
- 即使在低温下,单环和三环旋转异构体之间也会发生快速的相互转换.
- 基酸的独特"滑动"机制,而不是分离,促进了过渡.
结论:
- 探索的系统可以轻松进入多个旋转状态.
- 配体的可溶性和旋转状态的切换是内在的联系.
- 这项工作提供了一个详细的机械和热力学地图的旋转同位素相互转换在 hemilabile 复合体.
相关概念视频
Structural Isomerism
22.5K
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...
22.5K
Colors and Magnetism
14.7K
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...
14.7K
Stereoisomerism
14.7K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
14.7K
Valence Bond Theory
11.7K
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...
11.7K
Metal-Ligand Bonds
25.6K
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...
25.6K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
1.7K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
1.7K


