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Lanthanide Contraction: What is Normal?

Inorganic chemistry·2023
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The Lanthanide Contraction: What is Abnormal and Why?

Robert B Jordan1

  • 1Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.

Inorganic Chemistry
|January 28, 2025
PubMed
Summary

The lanthanide contraction

Area of Science:

  • Inorganic Chemistry
  • Lanthanide Chemistry
  • Coordination Chemistry

Background:

  • Lanthanide contraction describes the decrease in ionic radii across lanthanide series.
  • The Ln-Y bond distance typically decreases linearly with 4f electron count (n).
  • Anomalies in this trend (large or small Δ') have been observed.

Purpose of the Study:

  • Investigate the causes of anomalous lanthanide contraction trends.
  • Explain variations in the Ln-Y bond distance (Δ').
  • Determine conditions for consistent donor atom radii (r(Y)).

Main Methods:

  • Analysis of existing crystallographic data.
  • Correlation of Ln-Y distances with electronic structure.
  • Examination of structural factors influencing bond lengths.

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Main Results:

  • Large Δ' is attributed to extended Ln-Y distances in early lanthanides.
  • Small Δ' arises from chelate effects and intramolecular hydrogen bonding.
  • Consistent donor atom radii are achievable under specific conditions.

Conclusions:

  • Structural factors significantly impact lanthanide contraction anomalies.
  • Understanding these factors is crucial for predicting lanthanide behavior.
  • Results offer insights into normal and inverse trans influences.