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相关概念视频

Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

31.8K
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...
31.8K
Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

676
Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
676
Metal-Ligand Bonds02:51

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...
25.6K
Extraction: Advanced Methods00:56

Extraction: Advanced Methods

1.3K
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
1.3K
Structural Isomerism02:34

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...
22.4K
Valence Bond Theory02:42

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...
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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通过连接物结构变化扰乱铜氧化物单元

Debanjan Dhar1, Gereon M Yee1, Andrew D Spaeth1

  • 1Department of Chemistry, Center for Metals in Biocatalysis, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota , 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States.

Journal of the American Chemical Society
|December 24, 2015
PubMed
概括

新的铜复合物与修饰的配体影响原子抽象 (HAT) 反应. 电子调节影响热力学和动力学,揭示反应和速率之间的线性趋势,因障碍和道而有微妙的变化.

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Quantifying the Binding Interactions Between CuII and Peptide Residues in the Presence and Absence of Chromophores
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科学领域:

  • 有机金属化学
  • 催化剂
  • 反应机制

背景情况:

  • 铜复合物在催化过程中至关重要.
  • 了解对金属中心反应性的联体效应是关键.
  • 原子抽象 (HAT) 是一个基本的反应途径.

研究的目的:

  • 合成和表征具有量身定制的电子性质的新铜氧化物复合物.
  • 研究连接物修饰对HAT反应的热力学和动力学影响.
  • 阐明控制铜物种反应性的因素.

主要方法:

  • 新型配体组的合成: (pipMe) LH2 和 (NO2) LH2.
  • 对Cu (II) -OH2复合物的O-H键解离能量的测量.
  • 使用具有不同C-H结合强度的基质的Cu (III) 氧化物复合物的HAT反应的动力学研究.
  • 动态同位素效应 (KIEs) 的分析和过渡状态理论计算.

主要成果:

  • 对于O-H债券而言,这种修改导致了BDE的微小差异.
  • 在二次速率常数 (log k) 和反应度 (ΔH) 之间观察到线性相关性.
  • 反应速率的微妙变化归因于HAT屏障高度的变化和在低温 (-80至-20°C) 的量子道效率.

结论:

  • 通过连接体设计对铜复合体的电子调节对HAT反应热力学和动力学产生重大影响.
  • 观察到的线性趋势凸显了反应度的主导作用,但道化等其他因素也起到了作用.
  • 这项研究为控制氧化铜复合物的反应性提供了宝贵的见解.