Issue 41, 2018

Synthesis and molecular structure of pentadienyl complexes of the rare-earth metals

Abstract

The coordination chemistry of the sterically encumbered pentadienyl ligand pdl′ (pdl′ = 2,4-(Me3C)2C5H5) towards a series of rare-earth metals was systematically explored and the resulting metal complexes were fully characterized by several techniques including X-ray diffraction, elemental analysis, NMR spectroscopy and solid-state magnetic susceptibility studies. Three different reaction products were isolated depending on the redox-potentials and ionic radii of the metal atoms. They can be classified as (a) salt-metathesis, (b) metal reduction–ligand oxidation and (c) ligand deprotonation products. While for the larger and difficult to reduce metal ions, M = La, Ce, Pr and Nd, trivalent compounds [(η5-pdl′)3M] (1-M) were isolated, for the more readily reduced metal ions the corresponding divalent compounds [[(η5-pdl′)2M(thf)n] (2-M; with M = Sm (n = 2); Eu, Yb (n = 1)) were formed. A more complex structural motif was observed for the smaller and also difficult to reduce metal ions, M = Sc, Y, Gd, Tb, Dy, Ho, Er, Tm and Lu, which yielded the bimetallic complexes of the type [(pdl′)(pdl′−1H)(pdl′−2H)M2(thf)2] (3-M). In these dimeric complexes the pdl′ ligand acts as a result of deprotonation reactions not only as a monoanionic [pdl′], but also as a dianionic [pdl′−1H]2− and a trianionic [pdl′−2H]3− ligand scaffold, which form unusual structural motifs including a six-membered metallacycle. Solid-state magnetic susceptibility studies revealed the expected free-ion magnetic moments at T = 300 K for all investigated compounds, whereas at lower temperatures crystal-field effects dominate. Furthermore, for 3-Gd, 3-Tb, 3-Dy and 3-Er weak ferromagnetic exchange interactions were observed at low temperature.

Graphical abstract: Synthesis and molecular structure of pentadienyl complexes of the rare-earth metals

Supplementary files

Article information

Article type
Paper
Submitted
31 ⵢⵓⵍ 2018
Accepted
29 ⵖⵓⵛ 2018
First published
07 ⵛⵓⵜ 2018

Dalton Trans., 2018,47, 14468-14482

Synthesis and molecular structure of pentadienyl complexes of the rare-earth metals

J. Raeder, M. Reiners, R. Baumgarten, K. Münster, D. Baabe, M. Freytag, P. G. Jones and M. D. Walter, Dalton Trans., 2018, 47, 14468 DOI: 10.1039/C8DT03123A

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