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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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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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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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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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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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Chelating chloride using binuclear lanthanide complexes in water.

Carlson Alexander1, James A Thom1, Alan M Kenwright2

  • 1Chemistry Research Laboratory, Department of Chemistry, University of Oxford 12 Mansfield Road Oxford OX1 3TA UK stephen.faulkner@chem.ox.ac.uk.

Chemical Science
|February 9, 2023
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Summary
This summary is machine-generated.

Lanthanide complexes effectively bind chloride ions in water, overcoming hydroxide interference. This breakthrough offers new possibilities for chloride recognition in biological and chemical applications.

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Area of Science:

  • Anion coordination chemistry
  • Supramolecular chemistry
  • Lanthanide chemistry

Background:

  • Halide recognition in aqueous media is challenging for supramolecular receptors and coordination complexes.
  • Developing selective anion sensors for biological and environmental applications remains a key research area.

Purpose of the Study:

  • To investigate chloride binding in water and competing media using pre-organized binuclear lanthanide complexes.
  • To assess the efficacy of flexible spacers in modulating complex stability and anion binding.
  • To explore the potential of these complexes for anion recognition in complex environments.

Main Methods:

  • Synthesis of binuclear lanthanide complexes ([Ln2(DO3A)2C-2] and [Ln2(DO3A)2C-3]) with flexible spacers.
  • Spectroscopic and binding studies to determine chloride association constants in aqueous and buffered solutions.
  • Investigation of competing anion effects, particularly hydroxide ions at varying pH.

Main Results:

  • The synthesized lanthanide complexes exhibit chloride binding with apparent association constants up to 10^5 M^-1 in water.
  • Hydroxide bridging was observed at basic pH but was successfully displaced by chloride ions.
  • The complexes demonstrated stability and binding capability in both pure water and buffered systems.

Conclusions:

  • Pre-organized binuclear lanthanide complexes with flexible linkers are effective chloride binders in aqueous media.
  • These complexes show promise for selective chloride recognition, even in the presence of hydroxide ions.
  • This work opens a new avenue in anion coordination chemistry for applications in sensing and beyond.