ISSN:
0044-2313
Keywords:
Rare-Earth Complexes
;
Syntheses
;
Crystal Structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI2(THF)5]+I3-, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]-, [ErCl3(DME)2], and [Na(18-Crown-6)(THF)2]+[YbBr4(THF)2]-[LaI2(THF)5]+I3- (1) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at -83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way.[SmCl3(THF)4] (2) originates as colourless crystals on heating SmCl3 with excess THF in the presence of Me3SiNPEt3. Space group P21/c, Z = 8, lattice dimensions at -50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way.[ErCl2(THF)5]+[ErCl4(THF)2]- (3). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at -50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom.[ErC13(DME)2] (4) originates as pink single crystals from 3 with excess boiling 1,2-dimethoxyethane. Space group P21/c, Z = 4, lattice dimensions at -50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions.[Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]- (5) is formed as by-product by the reaction of YbBr3 with NaN(SiMe3)2 in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1, Z = 1, lattice dimensions at -70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr4(THF)2]-ions, in which the THF molecules are arranged in trans-position.
Notes:
[LaI2(THF)5]+I3- (1) wird aus Lanthanpulver und 1,2-Diiodethan in THF unter Lichteinwirkung als rote Kristalle erhalten. Raumgruppe Pbcn, Z = 4, Gitterkonstanten bei -83°C: a = 1264,9; b = 2218,9; c = 1199,1 pm; R = 0,031. Das Lanthanatom des Kations von 1 ist pentagonal-bipyramidal koordiniert mit den Iodatomen in den Axialpositionen.[SmCl3(THF)4] (2) entsteht beim Erhitzen von SmCl3 mit überschüssigem THF in Gegenwart von Me3SiNPEt3 als farblose Einkristalle. Raumgruppe P21/c, Z = 8, Gitterkonstanten bei -50°C: a = 3092,7; b = 826,2; c = 1758,3 pm; β = 93,85°; R = 0,054. 2 bildet wie das bereits bekannte, in der Raumgruppe F2dd kristallisierende Präparat, monomere Moleküle, in denen das Samariumatom verzerrt pentagonal-bipyramidal koordiniert ist mit zwei Chloratomen in den Axialpositionen.[ErCl2(THF)5]+ [ErCl4(THF)2]- (3). Blaßrosa Einkristalle von 3 erhielten wir nach der literaturbekannten Methode durch Reaktion von Erbiumpulver mit Trimethylchlorsilan und Methanol in THF. Raumgruppe C2/c, Z = 4, Gitterkonstanten bei -50°C: a = 1246,3; b = 1145,7; c = 2726,0 pm; β = 91,293°; R = 0,036. Das Erbiumatom des Kations von 3 hat pentagonal-bipyramidale Koordination mit den Chloratomen in den Axialpositionen, im Anion befinden sich die THF-Moleküle in der trans-Anordnung des oktaedrisch koordinierten Erbiumatoms.[ErCl3(DME)2] (4) entsteht als rosa Einkristalle aus 3 mit überschüssigem, siedendem 1,2-Dimethoxyethan. Raumgruppe P21/c, Z = 4, Gitterkonstanten bei -50°C: a = 1137,2; b = 886,5; c = 1561,1 pm; β = 104,746°; R = 0,032. 4 bildet monomere Moleküle, in denen das Erbiumatom verzerrt pentagonal-bipyramidale Umgebung hat mit zwei Chloratomen in den Axialpositionen.[Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]- (5) entsteht als Begleitprodukt bei der Umsetzung von YbBr3 mit NaN(SiMe3)2 in THF in Gegenwart von 18-Krone-6 als farblose Kristalle. Raumgruppe P1, Z = 1, Gitterkonstanten bei -70°C: a = 934,6; b = 988,9; c = 1208,0 pm; α = 73,82°; β = 72,98°; γ = 76,89°; R = 0,029. 5 enthält isolierte [YbBr4(THF)2]--Ionen, in denen die THF-Moleküle in trans-Stellung angeordnet sind.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19976230918
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