Direct reaction of iodine-activated lanthanoid metals with 2,6-diisopropylphenol

Shima Hamidi, Glen Berenger Deacon, Peter Courtney Junk, Paul Neumann

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Rare earth metals activated with ca. 2 iodine react directly with 2,6-diisopropylphenol (HOdip) in tetrahydrofuran (thf), 1,2-dimethoxyethane (dme), and dig-dme (dig = di(2-methoxyethyl) ether) to give solvated phenolate complexes [Ln(Odip)(3)(thf)(n)] (Ln = La, Nd, n = 3; Ln = Sm, Dy, Y, Yb, n = 2), [Eu(Odip)(mu-Odip)(thf)(2)](2), [Ln(Odip)(3)(dme)(2)] (Ln = La, Yb) and [La(Odip) 3(dig)] in good yield for Ln = La, Nd, Eu but modest yield for smaller Ln metals under comparable conditions. However, increasing the excess of metal greatly increased the yield for Ln = Y. The synthetic method has general potential, at least for lanthanoid phenolates. Comparison redox transmetallation/protolysis (RTP) reactions between Ln metals, Hg(C6F5)(2) and the phenol gave higher yields in shorter time and, for Eu, gave [Eu(Odip)(3)(thf)(3)] in contrast to an Eu-II complex from Eu(I-2). New [Ln(Odip)(3)(thf)(3)] complexes have fac-octahedral structures and [Ln(Odip)(3)(thf)(2)] monomeric five coordinate distorted trigonal bipyramidal structures with apical thf ligands. [Eu(Odip)(mu-Odip)(thf)(2)](2) is an unsymmetrical dimer with two bridging Odip ligands. One five coordinate Eu atom has distorted trigonal bipyramidal stereochemistry and the other is distorted square pyramidal. Whilst [La(Odip)(3)(dme)(2)] has irregular seven coordination with mer-Odip and chelating dme ligands, [Ln(Odip)(3)(dme)(2)] (Ln = Dy, Y (prepared by ligand exchange), Yb) are monomeric six coordinate with one chelating and one unidentate dme. A six coordinate fac-octahedral arrangement is observed in [La(Odip)(3)(dig)].
Original languageEnglish
Pages (from-to)3541 - 3552
Number of pages12
JournalDalton Transactions
Issue number12
Publication statusPublished - 2012

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