Direct Reactions of Iodine-Activated Rare-Earth Metals with Phenols of Varying Steric Bulk

作者：Deacon Glen B^*; Hamidi Shima; Junk Peter C; Kelly Rory P; Wang Jun

来源：European Journal of Inorganic Chemistry, 2014, 2014(3): 460-468.

DOI：10.1002/ejic.201301362

• Lanthanides
• Rare earths
• Iodine
• Steric hindrance
• Phenolates

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), [Ln(2)(Omes)(6)(thf)(4)] (Ln = La, Nd), [Y(Omes)(3)(thf)(3)] and [Eu-3(Omes)(6)(thf)(6)] in reactions controlled both by the bulk of the phenol and of the metal. It was noteworthy that Eu-II 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)]center dot 2MeCN, [Eu(Odpp)(2)(dme)(2)] and [Eu(Odpp)(3)(dme)], and a new polymorph of [Eu(Odbmp)(2)(thf)(3)]center dot thf, were determined.

• 出版日期2014-1