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Published on: April 14, 2020
Bond-valence parameters of lanthanides.
Agata Trzesowska1, Rafal Kruszynski, Tadeusz J Bartczak
1Department of X-ray Crystallography and Crystal Chemistry, Institute of General and Ecological Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland. agatat@p.lodz.pl
This study computed bond-valence parameters for lanthanide (Ln) coordination complexes, revealing trends based on Ln oxidation state and atomic number. These parameters help verify lanthanide oxidation states in various compounds.
Area of Science:
- Inorganic Chemistry
- Solid-State Chemistry
- Materials Science
Background:
- Bond-valence parameters are crucial for understanding chemical bonding and structure in inorganic compounds.
- Lanthanide elements exhibit diverse oxidation states beyond the common +3, influencing their chemical properties.
- Accurate determination of lanthanide oxidation states is essential for predicting and controlling material properties.
Purpose of the Study:
- To compute and analyze bond-valence parameters for lanthanide (Ln) coordination complexes with Ln in non-trivalent oxidation states (Ce(IV), Sm(II), Eu(II), Yb(II)).
- To investigate the relationship between bond-valence parameters and lanthanide oxidation state, atomic number, and coordinating atoms (O, N, Cl, S, C).
- To assess the utility of bond-valence parameters in verifying assigned lanthanide oxidation states in coordination compounds.
Main Methods:
- Calculation of Ln-O, Ln-N, Ln-Cl, Ln-S, and Ln-C(pi-bonded) bond-valence parameters for lanthanide coordination complexes.
- Systematic analysis of computed parameters in relation to lanthanide oxidation state and atomic number.
- Comparison of calculated bond-valence sums with known oxidation states to identify discrepancies and confirm assignments.
Main Results:
- Established a general order of bond-valence parameters: Ln-O > Ln-C > Ln-N > Ln-Cl > Ln-S.
- Observed a decrease in bond-valence parameter values with increasing lanthanide atomic number in coordination compounds.
- Demonstrated that Ln-O and Ln-N bond-valence parameters decrease with increasing lanthanide oxidation state.
- Identified instances of potentially incorrect lanthanide oxidation state assignments and cases confirmed by bond-valence calculations.
Conclusions:
- Bond-valence parameters provide valuable insights into the bonding characteristics of lanthanides in various oxidation states.
- The computed parameters offer a reliable method for validating lanthanide oxidation state assignments in coordination chemistry.
- This work contributes to a deeper understanding of lanthanide coordination chemistry and the application of the bond-valence model.
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