Reactivity of “Eu(OiPr)2” with Phenols: Formation of Linear Eu3, Square Pyramidal Eu5, Cubic Eu8, and Capped Cubic Eu9 Polymetallic Europium Complexes
- 6 July 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 39 (15) , 3213-3220
- https://doi.org/10.1021/ic9909532
Abstract
The direct reaction of europium with 2-propanol and phenols has been investigated under a variety of conditions. The reaction of europium metal with 2,6-dimethylphenol and 2,6-diisopropylphenol in 2-propanol at reflux revealed that polymetallic europium complexes could be generated by this method. Hx[Eu8O6(OC6H3Me2-2,6)12(OiPr)8], 1, and H5[Eu5O5(OC6H3iPr2-2,6)6(NCCH3)8], 2, were isolated by recrystallization in the presence of hexanes and acetonitrile, respectively, and characterized by X-ray crystallography. Complex 1 has a cubic arrangement of europium ions with face-bridging μ4-O donor atoms, edge-bridging μ-O(phenoxide/phenol) ligands, and terminal O(isopropoxide/2-propanol) ligands. Complex 2 is mixed valent and has a square pyramidal europium core with four Eu(II) ions at the basal positions and one Eu(III) ion at the apex. Since these reactions gave complicated mixtures of products from which 1 and 2 could only be obtained in low yields, direct reactions under less forcing reaction conditions were investigated. Europium reacts slowly at room temperature to form arene-soluble divalent [Eu(OiPr)2(THF)x]n, 3. Complex 3 reacts with 2,6-dimethylphenol to form the arene-insoluble complex {H[Eu(OC6H3Me2)2(OiPr)]}n, 4. Recrystallization of 4 in the presence of THF results in the crystallographically characterizable divalent trimetallic complex [Eu(OC6H3Me2-2,6)2(THF)2]3, 5, which has an unusual linear metal geometry. In the presence of HOiPr at ambient conditions in the glovebox, crystals of 5 slowly convert to the mixed valent H10[Eu8O8(OC6H3Me2-2,6)10(OiPr)2(THF)6], 6, which was found to have a cubic arrangement of europium atoms similar to 1 by X-ray crystallography. Complex 4, upon heating under vacuum, followed by reaction with THF, forms the arene-soluble divalent complex H18{[Eu9O8(OC6H3Me2-2,6)10(THF)7][Eu9O9(OC6H3Me2-2,6)10(THF)6]}, 7, which contains two types of capped cubic arrangements of europium ions in the solid state.Keywords
This publication has 25 references indexed in Scilit:
- Utility of 2-Methoxyethanol in the Synthesis of Polyeuropium Complexes: {[Eu(OCH2CH2OMe)2(OC6H3R2-2,6)-][H+]}4 (R = Me, iPr) and [EuAl2(OCH2CH2OMe)3Me5]2Inorganic Chemistry, 1998
- Unexpected Synthetic Routes to Lanthanide Chalcogenido Clusters: Sm8Se6(SePh)12(THF)8 and [Sm7S7(SePh)6(DME)7]+Journal of the American Chemical Society, 1997
- Substituent effects in the formation of aryloxide-bridged europium complexesJ. Chem. Soc., Dalton Trans., 1997
- Synthesis and characterisation of lanthanide(II) aryloxides including the first structurally characterised europium(II) compound [Eu(OC6H2But2-2,6-Me-4)2(thf)3]·thf (thf = tetrahydrofuran)J. Chem. Soc., Dalton Trans., 1995
- A dimeric calcium siloxide lightly stabilized by ammonia ligandsInorganic Chemistry, 1993
- Organoamido- and Aryloxo-Lanthanoids. V. Preparations of Low-Coordinate Lanthanoid(II) Phenolates, Ln (OC6H2But2-2,6-X-4)2( thf )n (Ln = Yb or Eu; X = H, Me or BuT; N = 2 or 3) and the X-Ray Crystal Structure of Five-Coordinate [Yb (OC6H2But2-2,6-X-4)2( thf )3].thfAustralian Journal of Chemistry, 1993
- Dinuclear barium alkoxides and siloxides displaying variable coordination numbers and asymmetric dispositions of ligandsInorganic Chemistry, 1992
- Divalent lanthanide chemistry. Preparation and crystal structures of sodium tris[bis(trimethylsilyl)amido]europate(II) and sodium tris[bis(trimethylsilyl)amido]ytterbate(II), NaM[N(SiMe3)2]3Inorganic Chemistry, 1984
- Synthesis and crystallographic characterization of a dimeric alkynide-bridged organolanthanide: [(C5H5)2ErC.ident.CC(CH3)3]2Inorganic Chemistry, 1981
- Synthesis and crystal structure of a neodymium isopropoxide chloride, Nd6[OCH(CH3)2]17ClInorganic Chemistry, 1978