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相关概念视频

Valence Bond Theory02:42

Valence Bond Theory

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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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Colors and Magnetism

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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...
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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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,...
49.5K
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Complexation Equilibria: The Chelate Effect01:19

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

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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...
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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
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减少和超减少的二复合物

Tania V Darnton1, Bryan M Hunter1, Michael G Hill2

  • 1Beckman Institute, California Institute of Technology , Pasadena, California 91125, United States.

Journal of the American Chemical Society
|April 13, 2016
PubMed
概括

这项研究表明,减少复合物加强了-的结合,使其成为一种强大的光氧化剂. 这项研究探讨了双核复合体中的电子转移.

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科学领域:

  • 无机化学
  • 电化学
  • 摄影化学

背景情况:

  • 双核复合物具有d(8) -d(8) 配置,它们的电子性质令人感兴趣.
  • 了解电子转移过程对于设计新型功能材料至关重要.

研究的目的:

  • 为了研究复合物的电化学还原 (d(8) -d(8) [Pt2(μ-P2O5(BF2) 4) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
  • 描述电子结构和降低时的粘合变化.
  • 评估母体和减少物种的光氧化特性.

主要方法:

  • 电化学技术 (循环电压测量) 用于研究还原潜力.
  • 电子磁共振 (EPR) 光谱分析减少的物种.
  • 电子结构的紫外线光谱和时间依赖密度函数理论 (TD-DFT) 计算.
  • 迈耶-米利肯债券订单计算以量化Pt-Pt债券.

主要成果:

  • 在 -1.68 V 和 -2.46 V 时观察到两个单电子减小,形成 Pt ((pop-BF2) ((5-) 和 Pt ((pop-BF2) ((6-).
  • 减少包括填充6pσ轨道,加强Pt-Pt和Pt-P键.
  • 在降低后,Pt-Pt债券订单从0.173增加到0.340.
  • 超减小的Pt{pop-BF2}{6-) 是一种罕见的6p{2) σ-键的双核复合体,尽管Pt-Pt距离有限.
  • 基因复合物被预测为一种强烈的光氧化剂,激发状态的电位为+1.57V (单体) 和+0.86V (三体).

结论:

  • 这项研究阐明了双核复合体中逐步减少的电子和结构后果.
  • 这些发现突显了这些复合物的强光氧化剂的潜力.
  • 这项研究有助于理解富含电子的多金属系统中的结合.