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DOI: 10.1039/A608062F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1181-1186

Homoleptic anionic aryloxolanthanoid(III) complexes

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Glen B. Deacon, Tiecheng Feng, Peter C. Junk, Brian W. Skelton and Allan H. White

Abstract

Several anionic complexes of lanthanoid metals with the 2,6-diphenylphenolate ligand have been synthesized and their room-temperature single-crystal structures determined. In novel reactions of anhydrous LnCl3 (Ln = Nd or Er) with NaOC6H3Ph2-2,6·0.5thf (thf = tetrahydrofuran) in 1,3,5-tri-tert-butylbenzene at 300 °C, complexes of the type [Na{Ln(OC6H3Ph2-2,6)4 }] were obtained. Crystallisation of [Na{Nd(OC6H3Ph2-2,6)4 }] from bis(2-methoxyethyl) ether (diglyme) or 1,2-dimethoxyethane (dme) afforded the corresponding solvated complexes [Na(diglyme)2][Nd(OC6H3Ph2 -2,6)4] or [Na(dme)3][Nd(OC6H3Ph2 -2,6)4] respectively, and from an analogous reaction for Ln = Er [Na(diglyme)2][Er(OC6H3Ph2 -2,6)4] was isolated. The complexes [Na(diglyme)2][Ln(OC6H3Ph2 -2,6)4] (Ln = Nd or Er) are isomorphous. Their structures revealed novel discrete homoleptic tetrakis(aryloxo)lanthanoid(III) anions, well separated from the solvated sodium cations. Annealing the reaction mixture for the synthesis of [Na{Nd(OC6H3Ph2-2,6)4 }] at 120 °C gave single crystals of a monomeric bimetallic in which the sodium ion is encapsulated by three aryloxide oxygens as well as by three phenyl rings of the phenolate ligand, and neodymium is surrounded by a highly distorted tetrahedral arrangement of aryloxide oxygens. There are also intramolecular π-Ph–M (M = Na or Nd) interactions.

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