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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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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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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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Complexometric Titration: Ligands00:43

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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...
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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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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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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Bimetallics in a Nutshell: Complexes Supported by Chelating Naphthyridine-Based Ligands.

Addison N Desnoyer1,2, Amélie Nicolay1,2, Pablo Rios1

  • 1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720-1460, United States.

Accounts of Chemical Research
|September 4, 2020
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Summary

This study introduces novel dinucleating 1,8-naphthyridine ligands for creating bimetallic catalysts. These catalysts, particularly dicopper complexes, show versatility in C-H activation and stability, aiding mechanistic studies in catalysis.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Catalysis

Background:

  • Bimetallic motifs are crucial in metalloenzymes and heterogeneous catalysts.
  • Complexity of bimetallic systems hinders fundamental property studies.
  • Need for well-defined models to understand bimetallic catalyst mechanisms.

Purpose of the Study:

  • To design and synthesize dinucleating 1,8-naphthyridine ligands for binding two transition metals.
  • To investigate the catalytic properties and mechanistic pathways of resulting bimetallic complexes.
  • To explore the influence of ligand design on heterobimetallic assembly.

Main Methods:

  • Synthesis of dinucleating 1,8-naphthyridine ligands.
  • Preparation of various bimetallic complexes, focusing on dicopper(I).
  • Characterization of complexes, including C-H activation studies and reaction with organic azides.
  • Oxidation and reduction studies to access different metal oxidation states.
  • Synthesis of heterobimetallic complexes using unsymmetrical ligands.

Main Results:

  • Dicopper(I) complexes exhibit versatile binding modes and engage in C-H bond activations.
  • Isolation of a stable dicopper triazolide intermediate, providing evidence for Cu-catalyzed azide-alkyne coupling (CuAAC) mechanism.
  • Access to mixed-valence Cu(I)Cu(II) and dicopper(II) complexes, as well as polynuclear copper hydride clusters.
  • Selective synthesis of heterobimetallic complexes through tailored ligand design.

Conclusions:

  • Dinucleating 1,8-naphthyridine ligands are effective platforms for studying bimetallic catalysis.
  • The developed dicopper complexes offer mechanistic insights into C-H activation and CuAAC.
  • Ligand design is a powerful tool for constructing diverse bimetallic and heterobimetallic assemblies with tunable properties.