在的协调球体中产生的二基酸 (II) 和相关的NHSi配体 (0)
Antje Meltzer1, Carsten Präsang, Matthias Driess
1Institute of Chemistry, Metalorganics and Inorganic Materials, Technische Universitat Berlin, Strasse des 17. Juni 135, Sekr. C2, D-10623 Berlin, Germany.
Journal of the American Chemical Society
|May 28, 2009
概括
研究人员合成了新的 ((II) 氧化物和可调节的NHSi配合剂,与相协调. 这些配体表现出可调节的供体/受体特性,为有机金属化学提供了新的可能性.
科学领域:
- 有机金属化学 有机金属化学
- 主群 化学 化学
背景情况:
- 基于的配体在协调化学中至关重要.
- 调整连接体的电子特性是催化剂设计的关键.
研究的目的:
- 为了合成和表征新的 (((II) 氧化物和NHSi配体.
- 为了研究这些连接体在复合体内的电子可调性.
主要方法:
- 合成NHSi-三碳烯复合物.
- 电友性添加水和其他试剂.
- 光谱表征 (NMR,IR) 和X射线晶体学.
主要成果:
- 第一个 (II) 氧化物和相关的NHSi配体的成功合成.
- 根据替代,证明了依附体的可调节的捐赠/接受能力.
- 易斯酸处理产生了PF(3) 类似的连接物,而水/酸添加产生了供体稳定复合物.
结论:
- 开发了具有可调节电子特性的新 ((II) 配体.
- 这些配体为设计具有量身定制特性的有机金属复合体提供了一个新的平台.
- 这些发现扩大了基配体在协调化学中的应用范围.
相关概念视频
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...
Coordination Compounds and Nomenclature
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Metal-Ligand Bonds
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...
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.
Crystal Field Theory - Tetrahedral and Square Planar Complexes
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...

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