Die Kristallstrukturen der Dysprosium-Komplexe [DyCl₃(DME)₂] und [DyCl₂(THF)₅]⁺[DyCl₄(THF)2]^- / Crystal Structures of the Dysprosium Complexes [DyCl₃(DME)₂] and [DyCl₂(THF)₅]⁺[DyCl₄(THF)₂]^-

Abstract

[DyCl3(DME)2] (DME = 1,2-dimethoxyethane) has been prepared from the known tetrahy-drofuran complex [Dy2Cl6(THF)7] in boiling DME. Both complexes were characterized by structure determinations. [DyCl3(DME)2]: Space group P21/c, Z = 4, lattice dimensions at -70 °C: a = 1141.9(6), b = 884.2(4), c = 1558.3(6) pm, β = 104.83(4)°. The complex has a molecular structure with a distorted pentagonal bipyramidal geometry in which the oxygen atoms of the chelating DME molecules and one chlorine atom occupy the pentagonal plane. [DyCl2(THF)5]+[DyCl4(THF)2]-: Space group C2/c, Z = 4, lattice dimensions at -70 °C: a -1241.4(9), b = 1139.4(6), c = 2735.1(19) pm, β = 91.19(4)°. The complex contains a seven-coordinate cation with axial chloride ligands in a pentagonal bipyramidal structure and a six-coordinate anion with a trans octahedral geometry.

A Convenient Route to Lanthanide Triiodide THF Solvates. Crystal Structures of LnI3(THF)4 [Ln = Pr] and LnI3(THF)3.5 [Ln = Nd, Gd, Y]

“…Crystallographically characterized THF adducts of the lanthanide trichlorides adopt a variety of structures in the solid state, including polymeric [LnCl 3 (THF) 2 ] n (Ln = Y, La, Ce, Pr, Nd), − monomeric LnCl 3 (THF) n (Ln = Yb, Lu, n = 3; Nd, Sm, Eu, Gd, n = 4), ,− dimeric [YbCl 3 (THF) 2 ] 2 , and the ion pair compounds [LnCl 2 (THF) 5 ][LnCl 4 (THF) 2 ] (Ln = Y, Gd, Dy, Er, Tb, Tm, Yb). ,,− The exact stoichiometry of the trichloride isolated appears to be dependent upon the ionic radius of the metal, the synthetic route employed, and the precise workup conditions. In contrast, only two structural types have been observed for THF adducts of the lanthanide triiodides: the seven-coordinate monomer LaI 3 (THF) 4 and the ion pairs [LnI 2 (THF) 5 ][LnI 4 (THF) 2 ] (Ln = Sm, Yb). , In order to investigate the influence of cation size on structure we set out to study the solid state structures of the triiodides obtained by the direct reaction of iodine with the metals described above.…”

Sterically Demanding Chelating Diamide Complexes of Yttrium and Lutetium

“…5 can be formally considered as a derivative of the ionic compound [LuCl 2 (THF) 5 ][LuCl 4 (THF) 2 ], in which all four chlorine atoms of the anion are substituted by 2 equiv of the {ArN(CH 2 ) 3 NAr} 2- ligand. Although the ionic compound [LuCl 2 (THF) 5 ][LuCl 4 (THF) 2 ] is so far not characterized by single-crystal X-ray diffraction, structures of [LnCl 2 (THF) 5 ][LnCl 4 (THF) 2 ] (Ln = Gd, Dy, Er, Tb) are known . Due to the already mentioned lesser steric demand of the {ArN(CH 2 ) 3 NAr} 2- ligand compared to (C 5 Me 5 ) - , the formation of an ate-complex is possible.…”

[NdI2(thf)5], the First Crystallographically Authenticated Neodymium(II) Complex

“…Similar seven‐coordinate structures were reported for the solvent adducts of samarium and ytterbium diiodide [SmI 2 (dme)(thf) 3 ],7 and [YbI 2 ( η 2 ‐dme) 2 ( η 1 ‐dme)] 8. Furthermore, the structures of the cationic lanthanide( III ) complexes [SmI 2 (thf) 5 ] + ,9a [LaI 2 (thf) 5 ] + ,9b [CeCl 2 (thf) 5 ] + ,9c [TbCl 2 (thf) 5 ] + ,9d [YbCl 2 (thf) 5 ] + ,9e,9f [GdCl 2 (thf) 5 ] + ,9e,9g [DyCl 2 (thf) 5 ] + ,9h,9i [ErCl 2 (thf) 5 ] + ,9b,9g and [LuCl 2 (thf) 5 ] + ,9j show an analogous arrangement, whereas for [YbI 2 (thf) 4 ]10 a six‐coordinate and for [SmI 2 (dme) 3 ]11 an eight‐coordinate structure was ascertained. Depending on the crystallization conditions, [SmI 2 (dme) 3 ] crystallizes either as an enantiomer ( Δ or Λ ) or as a racemic mixture.…”