Adventitiously Obtained Rare-Earth Peroxide Complexes and Their Structural Characterisation
Glen B. Deacon A , Craig M. Forsyth A , Dominique Freckmann A , Peter C. Junk B D , Kristina Konstas A , Jenny Luu A , Gerd Meyer C and Daniel Werner AA School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
B School of Pharmacy and Molecular Sciences, James Cook University, Townsville, Queensland 4811, Australia.
C Institute of Inorganic Chemistry, University of Cologne, Greinstraße 6, D-50939 Cologne, Germany.
D Corresponding author. Email: Peter.Junk@jcu.edu.au
Australian Journal of Chemistry 67(12) 1860-1865 https://doi.org/10.1071/CH14410
Submitted: 23 June 2014 Accepted: 29 July 2014 Published: 14 October 2014
Abstract
The structures of three adventitiously obtained peroxolanthanoid complexes have been determined, namely, [Yb2(Cp)4(μ-O)2/3(μ-O2)1/3(thf)2] (1) (Cp = cyclopentadienyl; thf = tetrahydrofuran), which has disorder between the bridging oxide and peroxide, [Nd2(o-PhPhForm)4(thf)4(μ-O2)] (2) (o-PhPhForm = N,N′-bis(2-phenylphenyl)formamidinate), and [Eu4(FForm)6(μ-OH)2(μ3-O2)2(μ-diglyme)2]·2diglyme (3) (FForm = N,N′-bis(2-fluorophenyl)formamidinate, diglyme = bis(2-methoxyethyl) ether). In the first two complexes, the peroxide bridges side-on between metals, whereas in the last complex, each peroxide bridges three metals through both oxygen atoms. The first complex was a single crystal amongst a bulk sample of [Yb(Cp)2(pzPh)(thf)] (pzPh = 2-(1′-pyrazolyl)phenyl), prepared by oxidation of dicyclopentadienylytterbium(ii) by bis(2-(1′-pyrazolyl)phenyl)mercury, the structure of which was also determined and showed distorted square planar stereochemistry for mercury.
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