螺旋体型双核 (IV) 复合物的层次组合
Markus Albrecht1, Sebastian Mirtschin, Marita de Groot
1Institut für Organische Chemie, RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany.
Journal of the American Chemical Society
|July 21, 2005
概括
研究人员研究了和复合体,发现二维结构在溶液和固态中是稳定的. 诸如电荷和连接体类型之类的因素会影响二元体的稳定性,从而表明有层次的自我组装.
科学领域:
- 协调化学 协调化学
- 超分子化学 超分子化学
- 材料科学 材料科学 材料科学
背景情况:
- 在协调研究中使用了4-7-H(2) 干.
- (IV) 和 (III) 离子被用来合成二次复合物.
研究的目的:
- 为了研究与和二元复合物的形成和稳定性.
- 了解影响溶液中单体/二元体平衡的因素.
- 探索复杂聚合物的自我组装机制.
主要方法:
- 用于固态结构分析的X射线晶体学.
- 核磁共振光谱和ESI FT-ICR MS用于解决方案研究.
- 双重质谱仪用于气相分解分析.
主要成果:
- 在固态中观察到三重桥式二极管.
- 在溶液中检测到一个单体/二元体平衡.
- 聚合物稳定性受到电荷,连接体供体强度,溶剂和固体阻碍的影响.
- 复合体表现出由非共价相互作用驱动的等级自我组装.
结论:
- 迪默的形成在热力学上是有利的.
- 在ESI FT-ICR中,MS揭示了二次体内的连接物交换机制.
- 由于电子性质和电荷,Ti和Ga复合体显示出不同的分解路径.
- 这些复合体作为等级自我组装的模型.
相关概念视频
Metallic 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...
Coordination Number and Geometry
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.
Structural Isomerism
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 be...
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 be...
Valence 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...
¹H NMR: Complex Splitting
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
¹H NMR: Pople Notation
The Pople nomenclature system classifies spin systems based on the difference between their chemical shifts. Coupled spins are denoted by capital letters with subscripts indicating the number of equivalent nuclei. When the coupled nuclei have well-separated chemical shifts, they are assigned letters that are far apart in the alphabet, such as A and X. When the difference in chemical shifts is small, coupled nuclei are named using adjacent letters of the alphabet (AB, MN, or XY).
A proton...
A proton...


