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The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′ 3 Ln compounds.
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This content will become publicly available on January 22, 2026
A comprehensive approach for elucidating the interplay between 4f n+1 and 4f n 5d 1 configurations in Ln 2+ complexes
To advance our ability to control the electronic properties of divalent lanthanides, the interplay between deformation densities, 4f interelectronic repulsion, and ligand field effects is discussed to predict the nature of their ground states.
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- Award ID(s):
- 2154255
- PAR ID:
- 10611690
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 16
- Issue:
- 4
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 2024 to 2033
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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