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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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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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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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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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Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
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Amidophenolate Lanthanide Complexes and Their Multielectron Reactivity.

Landon O King1, Kelly L Gullett1, Andrew W Mitchell1

  • 1H. C. Brown Laboratory, James Tarpo, Jr and Margaret Tarpo Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.

Inorganic Chemistry
|March 31, 2026
PubMed
Summary
This summary is machine-generated.

Redox-active ligands enable multielectron reactions in lanthanide complexes. New neodymium and ytterbium complexes with amidophenolate ligands react with sulfur, forming unique sulfur chains and metallocycles, demonstrating controlled electron transfer.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Lanthanide Chemistry

Background:

  • Achieving multielectron reactivity in redox-restricted lanthanide complexes often requires innovative strategies.
  • Redox-active ligands, such as iminoquinone (iq), facilitate electron transfer, enabling complex chemical transformations.
  • Previous work demonstrated the utility of the iminoquinone ligand in multielectron reactions across various metals.

Purpose of the Study:

  • To synthesize and characterize novel tris- and bis-ligated lanthanide complexes featuring the amidophenolate (ap) ligand.
  • To investigate the reactivity of these lanthanide complexes with elemental sulfur (S8).
  • To elucidate the ligand oxidation states and resulting structures formed during reactions with sulfur.

Main Methods:

  • Synthesis of tris-ligated lanthanide complexes [Nd(ap)3]K3 (Nd-L3) and [Yb(ap)3]K3 (Yb-L3), and a bis-ligated complex [Yb(ap)2]K (Yb-L2).
  • Reaction of Nd-L3 and Yb-L3 with elemental sulfur (S8).
  • Reaction of Yb-L2 with elemental sulfur (S8).
  • Characterization using 1H NMR spectroscopy, electronic absorption spectroscopy, and X-ray crystallography.

Main Results:

  • Treatment of Nd-L3 and Yb-L3 with S8 resulted in ligand oxidation, potassium iminosemiquinone ligand dissociation, and formation of a S72- chain.
  • Reaction of Yb-L2 with S8 led to ligand oxidation and the formation of a twist-boat metallocycle, [Yb(S5)(isq)2](K18c6) (Yb-S5).
  • Full characterization confirmed the assigned ligand oxidation states in all synthesized and reacted complexes.

Conclusions:

  • Lanthanide complexes with redox-active amidophenolate ligands exhibit controlled multielectron reactivity with elemental sulfur.
  • The nature of the lanthanide complex (tris- vs. bis-ligated) influences the outcome of the reaction with sulfur, leading to different sulfur species.
  • This study highlights the potential of redox-active ligands in designing lanthanide complexes for complex redox transformations and sulfur chemistry.