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- Title
Lanthanide(III) Sandwich and Half-Sandwich Complexes with Bulky Cyclooctatetraenyl Ligands: Synthesis, Structures, and Magnetic Properties.
- Authors
Lorenz, Volker; Liebing, Phil; Böhme, Michael; Buchholz, Axel; Plass, Winfried; Geue, Niklas; Hilfert, Liane; Busse, Sabine; Engelhardt, Felix; Hrib, Cristian G.; Edelmann, Frank T.
- Abstract
Five new lanthanide(III) sandwich and half-sandwich complexes with bulky cyclooctatetraenyl ligands have been prepared and fully characterized, including single-crystal X-ray structure determination. The treatment of anhydrous lanthanide(III) chlorides, LnCl3 (Ln = Pr, Tb, Yb), with 2 equivalents of Li2COT" [COT" = 1,4-bis(trimethylsilyl)cyclooctatetraene dianion] followed by crystallization in the presence of a coordinating solvent afforded the anionic sandwich complexes [Li(THF)4][Pr(COT")2] (1), [Li(DME)3][Tb(COT")2] (2; DME = 1,2-dimethoxyethane), and [Li(TMEDA)2][Yb(COT")2] (3; TMEDA = N,N,N',N'-tetramethylethylenediamine). Attempted oxidation of 2 with silver iodide did not afford the neutral terbium(IV) sandwich complex [Tb(COT")2]. Instead, the tri(µ-iodido)-bridged di-nuclear half-sandwich complex [Li(DME)2][Tb2(µ-I)3(COT")2] (4) was isolated in 72 % yield. In this complex, the Li(DME)2 fragment is attached to one of the µ-iodido ligands. A closely related binuclear lutetium complex, [Li(DME)3][Lu2(µ-Cl)3-(COTbig)2]·DME (5), was obtained by using the "superbulky" COTbig ligand [COTbig = 1,4-bis(triphenylsilyl)cyclooctatetraenyl dianion]. In addition to the spectroscopic and structural characterization, the magnetic properties of the paramagnetic terbium(III) derivative 2 have been investigated and further complemented by ab initio computational methods. These results have been used to discuss the structural requirements for potential terbium(III) single-ion magnets.
- Subjects
RARE earth metals; METAL complexes; MAGNETIC properties of metals; CHEMICAL synthesis; LIGANDS (Chemistry); SINGLE crystals; AB initio quantum chemistry methods
- Publication
European Journal of Inorganic Chemistry, 2017, Vol 2017, Issue 41, p4840
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201700878