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[Sn{9) Pt{2) }PPh{3) }{2) }-和[Sn{9) Ni{2) }CO}{3) }-复合体:两个截然不同的Sn{9) M{2) L过渡金属晶离子集群及其动态行为
Banu Kesanli1, James Fettinger, Donna R Gardner
1Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Journal of the American Chemical Society
|April 25, 2002
概括
合成了新的锡-和锡-集群. 这些新型集群表现出独特的结构和电子特性,包括溶液中的流动性行为和合成期间的C-H激活.
科学领域:
- 无机化学 无机化学 有机化学
- 有机金属化学 有机金属化学
- 材料科学 材料科学 材料科学
背景情况:
- 基于锡的集群由于其独特的电子结构和潜在应用而引起人们的兴趣.
- 复杂的聚离子集群的合成通常需要特定的反应条件和稳定剂.
研究的目的:
- 为了合成和表征新的锡-和锡-集群.
- 研究这些新型集群化合物的结构,电子和动态特性.
- 探索参与形成这些集群的反应机制.
主要方法:
- 使用金属化物 (K4Sn9) 和过渡金属前体 (Pt, Ni) 合成锡集群.
- 使用X射线衍射,NMR光谱 (119Sn,31P,195Pt),EPR光谱和ESI-MS进行了表征.
- 乳标记和化陷实验,以研究反应机制.
主要成果:
- 合成[Sn{9}Pt{2}PPh{3}]2- (2),一个具有C3v对称性的超密的10个顶点集群,通过溶剂的C-H激活形成.
- 合成[Sn(9) Ni ((2) ((CO) ]3- (3),一个具有C4v对称性的密闭的10个顶点集群,表现出对磁性和超细相互作用.
- 集群2在溶液中表现出流动性行为,内部分子交换与刚性Pt-Pt-PPh3棒相一致.
- 在ESI-MS分析中证实了两个群的父离子和各种相关物种的形成.
结论:
- 成功合成了具有独特结构和电子特性的新型锡过渡金属集群.
- -白金集群的形成涉及双重C-H激活通路.
- 锡集群的流动性行为为聚离子集群中的动态过程提供了洞察力.
相关概念视频
02:37Metallic 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...
02:57Coordination 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.
02:34Structural 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...
02:42Valence 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...
02:58Crystal Field Theory - Octahedral Complexes
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...
03:02Colors and Magnetism
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 eye.
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 eye.