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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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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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Metal-Ligand Bonds

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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...
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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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Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

27.3K
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...
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Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
2.4K
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
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Palladium(II) Weak-Link Approach Complexes Bearing Hemilabile N-Heterocyclic Carbene-Thioether Ligands.

Yuan Liu1, Zachary S Kean1, Andrea I d'Aquino1

  • 1Department of Chemistry and International Institute for Nanotechnology, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.

Inorganic Chemistry
|May 5, 2017
PubMed
Summary

Researchers developed new palladium(II) complexes with N-heterocyclic carbene-thioether ligands. These complexes linearly expand and contract, offering tunable control for advanced materials and supramolecular assemblies.

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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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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Area of Science:

  • Supramolecular Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Palladium(II) complexes with weak-link approach (WLA) ligands are known for their tweezer-like behavior.
  • Previous WLA complexes exhibit limited conformational flexibility.
  • Development of new ligand designs is crucial for expanding the utility of WLA complexes.

Purpose of the Study:

  • To report a novel class of homoligated palladium(II) WLA complexes.
  • To investigate their unique linear expansion and contraction behavior.
  • To explore their potential in constructing allosterically regulated supramolecular assemblies and materials.

Main Methods:

  • Synthesis of palladium(II) complexes with hemilabile N-heterocyclic carbene (NHC)-thioether ligands.
  • Chemical switching between trans open and trans closed states using chloride ions (Cl-).
  • Nuclear Magnetic Resonance (NMR) spectroscopy for solution-state configuration analysis.
  • Kinetic studies to determine isomerization barriers.

Main Results:

  • A new class of palladium(II) WLA complexes exhibiting linear configurational changes was synthesized.
  • Complexes can be reversibly switched between open and closed states by Cl- addition/extraction.
  • Unusual isomerization behavior was observed, with isolable anti,trans isomers at room temperature.
  • Tailorable linker lengths provide control over geometric changes during switching.

Conclusions:

  • The reported palladium(II) complexes offer a new platform for linear conformational switching.
  • Their tunable properties and isolable isomers open avenues for advanced supramolecular chemistry.
  • These complexes hold promise for the development of novel allosterically regulated materials.