Direct reactions of iodine-activated rare-earth metals with phenols of varying steric bulk

Deacon, Glen B., Hamidi, Shima, Junk, Peter C., Kelly, Rory P., and Wang, Jun (2014) Direct reactions of iodine-activated rare-earth metals with phenols of varying steric bulk. European Journal of Inorganic Chemistry, 2014 (3). pp. 460-468.

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Abstract

Sonication of rare-earth metals activated by iodine with 2,6-di-tert-butyl-4-methylphenol (HOdbmp), 2,6-diphenylphenol (HOdpp) and mesitol (HOmes) in acetonitrile or tetrahydrofuran (thf) yielded [La(Odbmp)3(NCMe)2], [Eu(Odbmp)2(thf)3], [Ln(Odpp)3(thf)2] (Ln = La, Nd), [Eu(Odpp)2(dme)2] (after workup with 1,2-dimethoxyethane), [Ln2(Omes)6(thf)4] (Ln = La, Nd), [Y(Omes)3(thf)3] and [Eu3(Omes)6(thf)6] in reactions controlled both by the bulk of the phenol and of the metal. It was noteworthy that EuII complexes were obtained under the conditions used. The method offers a general, environmentally friendly, metal-based route to rare-earth phenolates with prospects for wide application. Some comparison reactions of Ln metals with Hg(C6F5)2 and the phenols were also carried out and the additional complex [Eu(Odpp)3(dme)] was isolated. Structures of the new low-coordinate complexes [La(Odbmp)3(NCMe)2]·2MeCN, [Eu(Odpp)2(dme)2] and [Eu(Odpp)3(dme)], and a new polymorph of [Eu(Odbmp)2(thf)3]·thf, were determined.

Item ID: 31733
Item Type: Article (Refereed Research - C1)
Keywords: lanthanides, rare earths, iodine, steric hindrance, phenolates
ISSN: 1099-0682
Funders: Australian Research Council (ARC)
Date Deposited: 26 Feb 2014 09:57
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030206 Solid State Chemistry @ 10%
03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030299 Inorganic Chemistry not elsewhere classified @ 10%
03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030202 f-Block Chemistry @ 80%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 10%
97 EXPANDING KNOWLEDGE > 970110 Expanding Knowledge in Technology @ 10%
86 MANUFACTURING > 8611 Basic Metal Products (incl. Smelting, Rolling, Drawing and Extruding) > 861104 Basic Precious Metal Products @ 80%
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