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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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Donor Radii in Rare-Earth Complexes.

Charlene Harriswangler1, Juan C Frías2, M Teresa Albelda3,4

  • 1Centro Interdisciplinar de Química e Bioloxía (CICA) and Departamento de Química, Facultade de Ciencias, Universidade da Coruña, A Coruña 15071, Galicia , Spain.

Inorganic Chemistry
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Summary
This summary is machine-generated.

We developed new donor radii for rare-earth cations by analyzing structural data and theoretical calculations. These radii accurately predict metal-donor distances, aiding in understanding complex stability and reactivity.

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Area of Science:

  • Inorganic Chemistry
  • Solid-State Chemistry
  • Computational Chemistry

Background:

  • Rare-earth elements form diverse complexes with varying Ln-donor distances.
  • Accurate prediction of these distances is crucial for understanding chemical properties.

Purpose of the Study:

  • To establish a reliable set of donor radii for rare-earth cations.
  • To enable accurate prediction of Ln-donor bond distances.
  • To aid in the analysis of structural data and identification of bonding interactions.

Main Methods:

  • Analysis of structural data from the Cambridge Structural Database (CSD).
  • Theoretical calculations using density functional theory (DFT) and NEVPT2 wave function approaches.
  • Linear fitting of experimental bond distances to derive donor radii (rD).

Main Results:

  • Ln-donor distances correlate with cation and donor contributions.
  • Derived donor radii (rD) align with Shannon's crystal radii (CR).
  • Established rD values predict Ln-donor distances across different rare-earth cations and oxidation states.
  • Identified potential errors in existing X-ray structural assignments.

Conclusions:

  • The new donor radii provide a robust tool for predicting rare-earth cation-donor distances.
  • These radii enhance the interpretation of structural data, revealing interaction strengths.
  • The findings have significant implications for understanding the stability and reactivity of rare-earth metal ion complexes.