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Small cause - Great effect: What the 4f(n+1)5d(0) -> 4f(n)5d(1) configuration crossover does to the chemistry of divalent rare-earth halides and coordination compounds
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry.
2019 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 270, p. 324-334Article in journal (Refereed) Published
Abstract [en]

The rare-earth elements in the divalent state, i.e. with oxidation number + 2, may either have the electron configuration 4f(n+1)5d degrees(symbolized as R2+) or 4f(n)5d(1) (R(3+)e(-)). As R2+ (R = Eu, Yb, Sm, Tm, Dy, Nd) they can either be contained in extended solids as in the insulating diiodides RI2, or in coordination complexes such as samarocene, Kagan's reagent, or TmI2(DME)(3). In the case of R(3+)e(-), the "excess" d electron can either be delocalized and cause (semi)metallic behavior in extended solids, e.g. in LaI2, or localized with the R(3+)e(-) = 4f(n)5d(1) ion trapped in a coordination complex with (super)bulky ligands such as in [K(2.2.2-crypt)][LaCp ''(3)]. Thus, the seemingly small cause of a one-electron configuration crossover, 4f(n+1)5d degrees <--> Hf(n)5d(1) has a large effect on the chemical behavior and physical properties of the respective compounds where atomic properties and ligand effects play important roles.

Place, publisher, year, edition, pages
ACADEMIC PRESS INC ELSEVIER SCIENCE , 2019. Vol. 270, p. 324-334
Keywords [en]
Rare earth elements, Valence, Oxidation number, Configuration crossover
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-245153DOI: 10.1016/j.jssc.2018.10.050ISI: 000458344900042Scopus ID: 2-s2.0-85057389381OAI: oai:DiVA.org:kth-245153DiVA, id: diva2:1294920
Note

QC20190308

Available from: 2019-03-08 Created: 2019-03-08 Last updated: 2019-03-08Bibliographically approved

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