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Related Concept Videos

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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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: Factors Influencing Stability of Complexes01:09

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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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Metal-Ligand Bonds02:51

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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.
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Extraction: Advanced Methods00:56

Extraction: Advanced Methods

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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...
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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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P,N-Chelated Gold(III) Complexes: Structure and Reactivity.

Ann Christin Reiersølmoen1, Stefano Battaglia2, Andreas Orthaber3

  • 1Department of Chemistry, Norwegian University of Science and Technology, Høgskoleringen 5, 7491 Trondheim, Norway.

Inorganic Chemistry
|November 10, 2020
PubMed
Summary
This summary is machine-generated.

Researchers developed novel P,N-chelated gold(III) complexes, overcoming phosphorus oxidation challenges in gold catalysis. These versatile catalysts enable new synthetic transformations with controlled counterions, advancing homogeneous catalysis.

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Area of Science:

  • Organometallic Chemistry
  • Homogeneous Catalysis
  • Synthetic Chemistry

Background:

  • Gold(III) complexes are potent catalysts for diverse synthetic transformations.
  • Understanding the mechanisms of gold(III) catalysis, especially with phosphorus ligands, remains limited.
  • Phosphorus ligand oxidation by gold(III) has historically impeded their application in gold(III) catalysis.

Purpose of the Study:

  • To develop a method for generating P,N-chelated gold(III) complexes resistant to ligand oxidation.
  • To investigate the catalytic mechanisms of these novel gold(III) complexes.
  • To demonstrate their utility in key synthetic transformations.

Main Methods:

  • Generation of P,N-chelated gold(III) complexes with controlled counterions.
  • Characterization using NMR spectroscopy and X-ray crystallography.
  • Mechanistic studies employing density functional theory (DFT) calculations.

Main Results:

  • Successful synthesis of P,N-chelated gold(III) complexes, preventing AuCl4- formation.
  • Elucidation of the active catalyst formation mechanism.
  • Demonstration of catalytic activity in gold(III)-mediated styrene cyclopropanation and 1,6-enyne alkoxycyclization.

Conclusions:

  • P,N-chelated gold(III) complexes are readily synthesized and catalytically active.
  • These complexes overcome previous limitations associated with phosphorus ligand oxidation.
  • They offer a versatile platform for complex molecule synthesis via novel catalytic pathways.