F-electrons play a significant role in the chemistry of heavy transition metals
Multiple studies demonstrate that f-electrons (4f and 5f orbitals) play a fundamental and active role in determining the bonding, covalency, and structural properties of heavy transition and f-block elements.
The retrieved literature consistently supports the claim that f-electrons significantly influence the chemical bonding, electronic structure, and behavior of heavy elements (actinides and lanthanides), as shown through spectroscopic, quantum chemical, and first-principles analyses.
Hong B, Näder A, Sawallisch T, Bode T, Fichter S, Gericke R, Kaden P, Patzschke M, Stumpf T, Schmidt M, März J. Structure, Covalency, and Paramagnetism of Homoleptic Actinide and Lanthanide Amidinate Complexes.. 2024. https://doi.org/10.1021/acs.inorgchem.4c01901
The study highlights how 5f orbital occupations and covalency dictate bonding characteristics in actinide complexes.
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Beltran-Leiva MJ, Batista ER, Yang P. Unlocking Novel δ and φ Bonding Modes in Actinides via Oxidation State Control.. 2025. https://doi.org/10.1021/jacsau.4c01277
Research demonstrates that modifying actinide oxidation states alters f-orbital behavior, driving f-electron-mediated chemistries and back-bonding.
Ramanantoanina H, Schacherl B, Kovács A, Tagliavini M, Reynolds EM, Reitz C, Ekanayake RSK, Schäfer M, von Massow PV, Göttlicher J, Steininger R, Dardenne K, Haverkort MW, Benešová-Schäfer M, Vitova T. High-energy resolution X-ray spectroscopy reveals bonding characteristics of La<sup>3+</sup> homologues of actinium radiopharmaceuticals.. 2026. https://doi.org/10.1038/s42004-026-01929-4
Investigations into lanthanide and actinide homologues reveal that 4f and 5d orbital interactions and bond covalency play crucial roles in their electronic structures.
Xu X, Wang S, Yang X, Hu HS, Xiao C. Pressure-Induced Enhanced Covalency Difference in the Coordination of Am(III)/Eu(III) with an Unsymmetric Phenanthroline Extractant.. 2025. https://doi.org/10.1021/acs.inorgchem.5c00855
High-pressure studies show that f-orbitals (specifically 5f in americium) are highly sensitive, altering bond covalency and differences in f-block compounds.
Söderlind P, Landa A, Wu C, Swift D, Johansson B. First-principles theory for cerium predicts three distinct face-centered cubic phases.. 2025. https://doi.org/10.1038/s41598-025-03174-6
First-principles theory on cerium indicates that 4f-electron contributions dictate phase transitions and chemical bonding behavior under varying compressions.
Bai Z, Martelles MC, Sperling JM, Albrecht TE. Unveiling the covalency of versatile Pu(iii)-N bonds in a unique plutonium(iii) complex.. 2025. https://doi.org/10.1039/d5sc01808k
Analysis of plutonium complexes shows that delocalized 5f electrons drive unique nitrogen coordination affinities and bond covalency trends.
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