Lanthanoid and Alkaline Earth Complexes Involving New Substituted Pyrazolates

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doi:10.1071/CH12069

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Affiliated with RACI

Royal Australian
Chemical Institute

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-[Ln^II(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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