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Article << Previous     |     Next >>   Contents Vol 65(7)

Lanthanoid and Alkaline Earth Complexes Involving New Substituted Pyrazolates*

Glen B. Deacon A , Peter C. Junk A B and Aron Urbatsch A

A School of Chemistry, Box 23, Monash University, Clayton, Vic. 3800, Australia.
B Corresponding author. Email: peter.junk@monash.edu

Australian Journal of Chemistry 65(7) 802-810 http://dx.doi.org/10.1071/CH12069
Submitted: 2 February 2012  Accepted: 10 February 2012   Published: 30 April 2012


 
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Abstract

From the pyrazoles 3,5-di-(2′-furanyl)pyrazole (fu2pzH), 3-phenyl-5-(2′-thienyl)pyrazole (PhtpzH) and 3-(2′-furanyl)-5-(2′′-naphthyl)pyrazole (funappzH), a range of alkaline earth and lanthanoid pyrazolate complexes has been prepared by redox transmetallation/protolysis reactions between free metals, Hg(C6F5)2 and the pyrazoles, by reaction of I2-activated metals with the pyrazoles, and in one case by a similar reaction of unactivated metal, in the donor solvents tetrahydrofuran (thf) and 1,2-dimethoxyethane (dme). Thus the divalent [Ca(Phtpz)2(thf)4], [Ba(Phtpz)2(thf)4] and [Ca(funappz)2(thf)4]·(thf) complexes, the heteroleptic [Yb(Phtpz)I(thf)4] and the trivalent [La(fu2pz)3(thf)3]·2thf complex have been prepared and structurally characterized, as well as the dme complexes [Yb(Phtpz)2(dme)2] and [Eu(Phtpz)3(dme)2]. Highlights include the first trans-[LnII(pz)I(thf)4] complex, a rare transoid [Ln(pz)2(dme)2] complex and a complex with both chelating and unidentate dme. In all cases, the Phtpz complexes exhibit pronounced positional disorder of the 2-thienyl and phenyl groups in the solid state, as do the two polymorphs of the parent pyrazole.



Additional keywords: alkaline earth metals, crystal structure, disorder, lanthanides, pyrazolates.


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