Synthese und Kristallstrukturen der Seltenerd‐Komplexe [LaI₂(THF)₅]⁺I₃⁻, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]⁻, [ErCl₃(DME)₂] und [Na(18‐Krone‐6)(THF)₂]⁺ [YbBr₄(THF)₂]⁻

Abstract

Inhaltsfbersicht.[La12(THF)5]'13-(1) wird aus Lanthanpulver und 1,2-Diiodethan in THF unter Lichteinwirkung als rote Kristalle erhalten. Raumgruppe Pbcn, 2 = 4, Gitterkonstanten bei -83 "C: a = 1264,9; b = 2218,9; c = 1199,l pm; R = 0,031. Das Lanthanatom des Kations von 1 ist pentagonal-bipyramidal koordiniert rnit den Iodatomen in den Axialpositionen.[SmC13(THF)4] (2) entsteht beim Erhitzen von SmC13 rnit uberschussigem THF in Gegenwart von MesSiNPEt, als farblose Einkristalle. Raumgruppe P21/c, Z = 8, Gitterkonstanten bei -50 "C: a = 3092,7; b = 826,2; c = 1758,3 pm; /3 = 93,85"; R = 0,054. 2 bildet wie das bereits bekannte, in der Raumgruppe E d d kristallisierende Praparat, monomere Molekule, in denen das Samariumatom verzerrt pentagonalbipyramidal koordiniert ist mit zwei Chloratomen in den Axialpositionen. [ErC12(THF)5]'[ErC14(THF)2]-(3). BlaBrosaEinkristalle von 3 erhielten wir nach der literaturbekannten Methode durch Reaktion von Erbiumpulver mit Trimethylchlorsilan und Methanol in THE Raumgruppe C2k, 2 = 4, Gitterkonstanten bei -50 " C a = 1246,3; b = 1145,7; c = 2726,O pm; /3 = 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-Molekiile in der trans-Anordnung des oktaedrisch koordinierten Erbiumatoms. [ErC13(DME)2] (4) entsteht als rosa Einkristalle aus 3 rnit uberschussigem, siedendem 1,2-Dimethoxyethan. Raumgruppe P21/c, 2 = 4, Gitterkonstanten bei -50 " C a = 1137,2; b = 886,5; c = 1561,l pm; /3 = 104,746'; R = 0,032. 4 bildet monomere Molekule, in denen das Erbiumatom verzerrt pentagonal-bipyramidale Umgebung hat mit zwei Chloratomen in den Axialpositionen. [N~(~~-K~O~~-~)(THF)~]+[Y~B~~(THF)~] (5) entsteht als Begleitprodukt bei der Umsetzung von YbBr3 mit NaN(SiMe& in THF in Gegegwart von 18-Krone-6 als farblose Kristalle. Raumgruppe P1, Z = 1, Gitterkonstanten bei -70 "C: a = 934,6; b = 988,9; c = 1208,O pm; a = 73,82"; /3 = 72,98"; y = 76,89"; R = 0,029. 5 enthalt isolierte [YbBr4(THF)J-Ionen, in denen die THF-Molekule in trans-Stellung angeordnet sind. Syntheses and Crystal Structures of the Rare-Earth Complexes [La12(THF)5]+13-, [ SmC13(THF)4], [ ErC12( THF)$ [ ErC14(THF)2]-, [ ErCl3(DME)2], and Abstract.[La12(THF)5]+13-(1) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, 2 = 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 the iodine atoms in the axial positions in a pentagonal-bipyramidal way.

[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.…”

Bis(salicylato)borate as Versatile Sensitizer for Highly Luminescent Lanthanide Oxoborates from the Ultraviolet to Near Infrared with 4f and 5d Participation of the Lanthanides

“…The Er–Cl interatomic distances of 255.6(2) and 257.6(2) pm are in good agreement with the Er–Cl distances found, for example, in [ErCl 2 {(Ph 2 P)N}(thf) 3 ] (Er–Cl 257.2–258.3 pm) or [ErCl 2 (thf) 5 ][ErCl 4 (thf) 2 ] (Er–Cl 255.4–259.8 pm) . The Er–O distance of 230.3(2) pm is also in good agreement with the known Er–O distances in [Er(Cy 3 PO) 2 (H 2 O) 5 ] (Er–O 220.7–235.8 pm), and the Er–N distances in the range 248.3(3)–252.0(3) pm are in good accordance with those in [Er(dien) 2 AsS 4 ] (dien = diethylenetriamine; Er–N 248.0–254.5 pm) and the Er III complex of the Schiff base N , N′ ‐bis(3,5‐dichlorosalicylidene)‐(1 S ,2 S )‐1,2‐cyclohexylenediamine (Er–N 249.6–252.8 pm) .…”

[AnI3(THF)4] (An = Np, Pu) Preparation Bypassing An0 Metal Precursors: Access to Np3+/Pu3+ Nonaqueous and Organometallic Complexes

“…Furthermore, the elimination of I 2 in some solvent systems can be problematic due to [I 3 ] − salt formation; indeed, [PuI 2 (THF) 4 (py)][I 3 ] was isolated from the reaction of [PuI 3 (py) 4 ] with I 2 in THF, in the presence of t BuNH 2 . 52 While examples also exist in lanthanide chemistry, 87,88 there is an excellent precedent for this issue being obviated in the synthesis of [LnI 3 (Et 2 O) 3 ] (Ln = Ce, Pr, Nd, Sm, Gd, Tb, and Tm) by using Et 2 O as the reaction medium. 89 As described in Scheme 4 and in more detail below, the use of Et [PuI 3 (THF) 4 ] (3-Pu) were isolated in excellent microcrystalline yield (Np = 249 mg, >99%; Pu = 91 mg, 94%with respect to starting material An-elemental content) by warming the crude powders in THF, followed by precipitation with pentane and then drying in vacuo.…”