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Cited by 388

The DOI matches its Crossref record; 33 of the 33 references it cites were found in a registry or an index.

Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr2+, Gd2+, Tb2+, and Lu2+

MacDonald, Matthew R., Bates, Jefferson E., Ziller, Joseph W., Furche, Filipp, Evans, William J.·2013·Journal of the American Chemical Society
DOI 10.1021/ja403753j
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Abstract

The first examples of crystallographically characterizable complexes of Tb(2+), Pr(2+), Gd(2+), and Lu(2+) have been isolated, which demonstrate that Ln(2+) ions are accessible in soluble molecules for all of the lanthanides except radioactive promethium. The first molecular Tb(2+) complexes have been obtained from the reaction of Cp'3Ln (Cp' = C5H4SiMe3, Ln = rare earth) with potassium in the presence of 18-crown-6 in Et2O at -35 °C under argon: [(18-crown-6)K][Cp'3Tb], {[(18-crown-6)K][Cp'3Tb]}n, and {[K(18-crown-6)]2(μ-Cp')}{Cp'3Tb}. The first complex is analogous to previously isolated Y(2+), Ho(2+), and Er(2+) complexes, the second complex shows an isomeric structural form of these Ln(2+) complexes, and the third complex shows that [(18-crown-6)K](1+) alone is not the only cation that will stabilize these reactive Ln(2+) species, a result that led to further exploration of cation variants. With 2.2.2-cryptand in place of 18-crown-6 in the Cp'3Ln/K reaction, a more stable complex of Tb(2+) was produced as well as more stable Y(2+), Ho(2+), and Er(2+) analogs: [K(2.2.2-cryptand)][Cp'3Ln]. Exploration of this 2.2.2-cryptand-based reaction with the remaining lanthanides for which Ln(2+) had not been observed in molecular species provided crystalline Pr(2+), Gd(2+), and Lu(2+) complexes. These Ln(2+) complexes, [K(2.2.2-cryptand)][Cp'3Ln] (Ln = Y, Pr, Gd, Tb, Ho, Er, Lu), all have similar UV-vis spectra and exhibit Ln-C(Cp') bond distances that are ~0.03 Å longer than those in the Ln(3+) precursors, Cp'3Ln. These data, as well as density functional theory calculations and EPR spectra, suggest that a 4f(n)5d(1) description of the electron configuration in these Ln(2+) ions is more appropriate than 4f(n+1).

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Metadata

Authors
MacDonald, M. R., Bates, J. E., Ziller, J. W., Furche, F., & Evans, W. J.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2013-05-22
Volume
135
Issue
26
Pages
9857-9868
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja403753j
OpenAlex
W2021628309
Cited by
388
References
33
FWCI
11.25
Type
journal article
Language
en
Open access
closed

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