Reactions Of LnCl3 Research Articles

Photoluminescence of Lanthanide-Titanium-Oxo Clusters Eu9Ti2 and Tb9Ti2 Based on a β-Diketone Ligand.

A series of acetylacetone-protected lanthanide-titanium-oxo clusters (LTOCs), formulated as [La6Ti(μ3-OH)8(acac)12(CH3O)2(CH3OH)6] (La6Ti; Hacac = acetylacetone) and [Ln9Ti2(μ4-O)(μ3-OH)14(acac)17(CH3O)2(CH3OH)3] [Ln = Eu (Eu9Ti2) and Tb (Tb9Ti2)], were synthesized through the reactions of LnCl3·6H2O (Ln = La, Eu, and Tb), Hacac, Ti(OiPr)4, and triethylamine in methanol. Crystal structural analysis shows that La6Ti exhibits an hourglass-like structure consisting of two La3Ti cubane subunits by sharing one Ti4+ ion, while Eu9Ti2 can be viewed as a combination of four Eu3Ti cubane subunits by sharing three corners and one side. The photoluminescence (PL) measurements show that Tb9Ti2 exhibits excellent PL properties with a high quantum yield (QY) of 34.8%, while Eu9Ti2 only has a QY of 1.4% because of the different photosensitizations of ligands to Eu3+ and Tb3+ ions in the photophysical process.

Crystallographic characterization of rare-earth cyano-tri-phenyl-borate complexes and the cyano-borates [NCBPh3]1-, [NCBPh2Me]1-, and [NCBPh2(μ-O)BPh2]1.

The investigation of the coordination chemistry of rare-earth metal complexes with cyanide ligands led to the isolation and crystallographic characterization of the Ln III cyano-tri-phenyl-borate complexes di-chlorido-(cyano-tri-phenyl-borato-κN)tetra-kis-(tetra-hydro-furan-κO)lanthanide(III), [LnCl2(C19H15BN)(C4H8O)4] [lanthanide (Ln) = dysprosium (Dy) and yttrium Y)] from reactions of LnCl3, KCN, and NaBPh4. Attempts to independently synthesize the tetra-ethyl-ammonium salt of (NCBPh3)- from BPh3 and [NEt4][CN] in THF yielded crystals of the phenyl-substituted cyclic borate, tetra-ethyl-aza-nium 2,2,4,6-tetra-phenyl-1,3,5,2λ4,4,6-trioxatriborinan-2-ide, C8H20N+·C24H20B3O3 - or [NEt4][B3(μ-O)3(C6H5)4]. The mechanochemical reaction of BPh3 and [NEt4][CN] without solvent produced crystals of tetra-ethyl-aza-nium cyano-diphenyl-λ4-boranyl di-phenyl-borinate, C8H20N+·C25H20B2NO- or [NEt4][NCBPh2(μ-O)BPh2]. Reaction of BPh3 and KCN in THF in the presence of 2.2.2-cryptand (crypt) led to a crystal of bis-[(2.2.2-cryptand)potassium] 2,2,4,6-tetra-phenyl-1,3,5,2λ4,4,6-trioxatriborinan-2-ide cyano-methyl-diphenyl-borate tetra-hydro-furan disolvate, 2C18H36KN2O6 +·C24H20B3O3 -·C14H13BN-·2C4H8O or [K(crypt)]2[B3(μ-O)3(C6H5)4][NCBPh2Me]·2THF. The [NCBPh2(μ-O)BPh2]1- and (NCBPh2Me)1- anions have not been structurally characterized previously. The structure of 1-Y was refined as a two-component twin with occupancy factors 0.513 (1) and 0.487 (1). In 4, one solvent mol-ecule was disordered and included using multiple components with partial site-occupancy factors.

Chloride-bridged, defect-dicubane {Ln4} core clusters: syntheses, crystal structures and magnetic properties.

Three chloride-bridged lanthanide compounds, [Ln4Cl6(CH3OH)12(OH)2]·4Cl·2CH3OH [Ln = Gd (), Dy () and Er ()], have been unexpectedly isolated by the reactions of LnCl3·6H2O and N,N'-bis(salicylidene)-1,2-(phenylene-diamine) (H2L). X-ray crystallographic analysis reveals a triclinic cell with a unique defect-dicubane {Ln4} core and the structure across this series is nominally isomorphic. Measurements of direct current magnetic susceptibility and isothermal magnetization give insight into the relevant cluster Hamiltonians for , , and , and alternating current susceptibility shows slow relaxation in , but not in or down to 2 K and up to 1 kHz.

Direct Synthesis of Ion‐pair Lanthanide Borohydrides and their High Activity for Polymerization of L‐Lactide and ϵ‐Caprolactone

AbstractThe reactions of LnCl3 (Ln = Nd, Pr, La) with NaBH4 in a THF solution at 75 °C afforded ion‐pair lanthanide borohydrides [Ln(BH4)2(THF)5]+[Ln(BH4)4(THF)2]– [Ln = Nd (1), Pr (2), La (3)] in high yields whilst similar reactions at 40 °C yielded the neutral borohydrides [Ln(BH4)3(THF)3] [Ln = Nd (4), Pr (5), La (6)]. The influence of the size of the lanthanide metals on the synthesis of ion‐pair lanthanide borohydrides was observed. The same procedure with the middle and latter lanthanide metal chlorides as that for the synthesis of 1–3 did not afford the analogous complexes, but the neutral lanthanide borohydrides [Ln(BH4)3(THF)3] [Ln = Sm (7), Eu (8), Yb (9)] were isolated. Complexes 1–3 showed high activity for the ring‐opening polymerizations of ϵ‐caprolactone (ϵ‐CL) and L‐Lactide (L‐LA). The comparable study on the reactivity between 1 and 4 revealed that 1 showed somewhat higher activity than 4 in all the polymerizations studied, but no quite difference in chemistry behavior between the two complexes.

Syntheses and characterizations of polymeric silver iodoplumbates, and iodoplumbates with lanthanide complexes

Novel heterometallic Ag–iodoplumbates [Ln(DMSO)8]Pb2Ag2I9 [Ln = La(1), Gd(2), Tm(3)] were prepared by reactions of LnCl3, PbI2, AgNO3 and KI in dimethyl sulfoxide (DMSO). The same reactions without reactant AgNO3 produced new iodoplumbates [Ln(DMSO)8][(DMSO)Pb4I11] [Ln = La(4), Pr(5), Nd(6)]. All Ln3+ ions are solvated with eight DMSO molecules in the reactions, forming [Ln(DMSO)8]3+ complex cations to act as counterions to the iodometallate anions. In compounds 1–3, two AgI4 tetrahedra and two PbI6 octahedra are connected into the 1D heterometallic Ag–Pb iodometallate [Ag2Pb2I9]n3n−via face-sharing. The [Ag2Pb2I9]n3n− anionic chains run parallel along the b axis in 1, and along the a axis in 2 and 3. The [Ln(DMSO)8]3+ cations are located between the chains. In compounds 4–6, two PbI6 and two PbI5O octahedra are interlinked end to end via sharing common faces to generate a 1D [(DMSO)Pb4I11]n3n− chain, which represents a new member of iodoplumbate aggregates. In the [(DMSO)Pb4I11]n3n− chain, the Pb2+ ions are joined not only via μ-I bridges, but also via μ-O bridges. The μ-O oxygen bridging has never been observed in iodoplumbates. Solid state optical absorption spectral analyses show optical band gaps in the range of 2.25–2.88 eV for compounds 1–6. Blue shift of the absorption edge caused by copolymerization of the AgI4 unit occurs on the iodoplumbates.

Reduction of LnIII to LnII in reactions of LnCl3·6H2O (Ln = Eu, Yb, and Sm) with Bui 2AlH in THF. The formation of soluble luminescent complexes LnCl2·xTHF

Soluble luminescent complexes of divalent lanthanides, LnCl2·xTHF (Ln = Eu, Yb, and Sm), were obtained for the first time by reduction of LnIII to LnII in reactions of the lanthanide trichloride hexahydrates LnCl3·6H2O with Bui 2AlH in THF. The photoluminescence spectra and other spectral characteristics of LnCl2·xTHF were examined.

Recent advances in trivalent f-element borate chemistry

The reactions of LnCl3 · 6 H2O with molten boric acid result in the formation of three different products depending on the identity of the lanthanide metal. The analogous reactions using AnCl3 · 6 H2O (An = Pu(III), Am(III), and Cm(III) with molten boric acid under the same conditions do not yield the same results as those of the 4f series or of the other 5f elements. For the most part, the actinide products obtained have no lanthanide analogues making them unique compounds. Furthermore, the reactions of LnX3 · yH2O (X = Br, I) (Ln = La-Nd) with molten boric acid results in the formation of two products. The analagous set of reactions was performed with PuX3 · yH2O (X = Br, I) which, yet again, gave rise to completely novel compounds. All of these compounds are three-dimensional framework structures comprised of sheets. These sheets are made up of both BO3 and BO4 units which are arranged in such a maner that creates triangular holes in which the lanthanide or actinide sites reside. The borate units of the triangular holes provide six oxygen atoms that coordinate in the equatorial region resulting in unique nine- and/or ten-coordinate geometries. The similarities and differences between the 4f and 5f borate compounds are discussed with particular emphasis on the periodic trends of this system.

Syntheses and Crystal Structures of Mononuclear and Binuclear Lanthanide Halide Complexes with Diglyme

AbstractTwo types of isostructural complexes of lanthanide chlorides with diglyme have been synthesized. These are mononuclear molecular complexes [LnCl3(diglyme)(THF)] (Ln = Eu (1), Gd (2), Dy (3), Er (4), Yb (5); diglyme = diethylen glycol dimethyl ether) and binuclear molecular complexes [LnCl3(diglyme)]2 (Ln = Dy (3d), Er (4d), Yb (5d)). Complex 1 was obtained by the reaction of [EuCl3(DME)2] with diglyme in THF. The complexes 2–5 and 3d–5d resulted from reactions of LnCl3·6H2O, (CH3)3SiCl and diglyme in THF. The mononuclear complexes 2–5 crystallized directly from the solutions where the reactions of lanthanide compounds with diglyme took place. Recrystallizations of the powder products of the same reactions from dichloromethane resulted in the binuclear complexes 3d–5d. Reactions of lanthanide bromide hydrates, (CH3)3SiBr and diglyme in THF achieved mononuclear molecular complexes [LnBr3(diglyme)(L)] (Ln = Gd, L = H2O (6); Ln = Ho, L = THF (7)). Crystals of 6 and 7 were grown by recrystallization from dichloromethane. The lanthanide atoms (Ln = Eu–Yb) are seven‐coordinated in a distorted pentagonal bipyramidal fashion in all reported complexes, 1–7 and 3d–5d. Four oxygen atoms and three halide ions are coordinated to lanthanide atoms in 1–7, [LnX3(diglyme)(L)]. Four chloride ions, two bridging and two nonbridging, and three oxygen atoms are coordinated to lanthanide atoms in 3d–5d, [LnCl3(diglyme)]2.

A new approach to the preparation of lanthanide catalysts for the synthesis of 2-propyl-3-ethylquinoline based on the reactions of LnCl3 · 6H2O crystalline hydrates with triisobutylaluminum

A new approach to the preparation of lanthanide catalysts for the synthesis of nitrogen heterocycles (exemplified by 2-propyl-3-ethylquinoline) was developed based on the reactions of LnCl3 · 6H2O crystalline hydrates with alkylaluminums. It was found that the interaction of LnCl3 · 6H2O (Ln = Ce, Pr, Tb, and Eu) with iso-Bu3Al in aromatic solvents (20°C) resulted in the formation of soluble (isobutane and the alumoxane (iso-Bu2Al)2O) and insoluble products (with the empirical formula LnCl3 · xH2O · y(iso-Bu2Al)2O (x = 0.4–0.7; y = 0.04–0.07)). The physiochemical properties of LnCl3 · xH2O · y(iso-Bu2Al)2O were studied, and these compounds were found to be highly efficient catalysts for the reaction of aniline condensation with butyraldehyde to form 2-propyl-3-ethylquinoline.

Syntheses, crystal structures and luminescent properties of two novel lanthanide/4-pya complexes: [Ln(4-pya)3(H2O)2]2 (Ln = Eu, La; 4-pya = trans-4-pyridylacrylate)

Reactions of Ln2O3 and trans-4-pyridylacrylic acid (4-Hpya) in EtOH/H2O or MeOH/H2O produced two new lanthanide/4-pya complexes [Ln(4-pya)3(H2O)2]2 (1: Ln=Eu; 2: Ln=La) in low yields. However, reactions of LnCl3·6H2O with 4-Hpya/aqueous ammonia in EtOH/H2O or MeOH/H2O gave rise to 1 or 2 in higher yields. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and X-ray analysis. Compounds 1·2EtOH·2H2O and 2·2MeOH·2H2O were confirmed to possess one-dimensional polymeric chain structures. In the structure of 1, each Eu(III) adopts a monocapped square-antiprism coordination geometry and each dimer [Eu(4-pya)3(H2O)2]2 within the chain is interconnected by two pairs of different bridging 4-pya ligands. On the other hand, each La(III) of 2 takes a bicapped square-antiprism coordination geometry and each dimer [La(4-pya)3(H2O)2]2 within the chain is linked by two pairs of tridentate bridging 4-pya ligands. The luminescent properties of 1 and 2 in the solid state were investigated.

Synthesis, structures and properties of a series of novel left- and right-handed metal coordination double helicates with chiral channels

The reactions of LnCl3 (Ln = lanthanide cations), L- or D-tartaric acid and molybdate in acidified aqueous solutions gave rise to the enantiopure left- or right-handed double helical coordination metal compounds, {A[Mo2VIO4LnIII(H2O)6(C4H2O6)2]·4H2O}n (Ln = Sm, Eu, Gd, Ho, Yb, Y; C4H2O6 = L- or D-tartaric acid; A = NH4 or H3O; MoLn represent all complexes), which have been characterized by single X-ray crystal structure analyses, IR, FT-Raman, TGA, XRPD, electric conductivity, EPR and magnetic susceptibility studies. The TGA and XRPD studies for compound MoGd suggest that the backbone is “collapsed” with the removement of aqua ligands and crystallization water molecules. However, it is easily reverted to the original compound after being immersed in water, as confirmed by similar XRPD patterns. The electric conductivity studies for these compounds reveal they are semiconductors. As aforementioned, the conductivity behaviors for the dry sample and reversed sample of MoGd are also very similar, in line with the XPRD results. Study of the magnetic susceptibilities reveal that the magnetic behaviors for MoGd, MoDy, MoHo and MoYb obey the Curie–Weiss law.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL CLASS OF HETEROBIMETALLIC DERIVATIVES OF YTTRIUM AND LANTHANIDES BASED ON {Zr2(OPr–i)8Cl}− UNITS

Heterobimetallic chloride isopropoxides of the type [Ln{Zr2(OPr-i)8Cl}2Cl] have been synthesised conveniently by the 1:4 reactions of LnCl3 · 3 i-PrOH (Ln = Y, La, Pr, Sm and Gd) with Zr(OPr-i)4 in benzene. All of these derivatives have been characterised by elemental analyses, spectroscopic (IR. 1H and 13C NMR) studies and molecular weight determinations.

Synthesis and Structure of Lanthanide Sandwich Complexes with Mixed Cyclooctatetraenyl and Chelating Substituted‐indenyl Ligands

AbstractTwo types of sandwich complexes (η5‐MeOCH2CH2C9H6) Ln (η8‐C8H8) (THF)n [Ln=La (1), Nd(2), n=0; Sm(3), Dy (4) and Er (5). n = l] and (η5‐C4H7OCH2C9H6)Ln(η8‐C8H8) (THF) [Ln = La (6), Nd(7). Sm(8). Dy (9) and Er (10)] were synthesized by the reactions of LnCl3 with equivalent mole of K2C8H8, followed by treatment with corresponding potassium salt of ether‐substituted indenide. The molecular structures of 3 and 8 were determined by single crystal X‐ray diffraction. (η5 ‐MeOCH2CH2C9H6) Sm (η8‐C8H8) (THF) (3) monoclinic. Pt1/c, a = 1.4793(3) nm, b = 0.8716 (2) nm, c = 1.6149 (3) nm, β = 98. 17(3), V = 2.0612(7) nm3, Z = 4, R(F)=0.0362. (η5‐C4H7OCH2C9H6)Sm(η8‐C8H8)(THF) (8) orthorhombic. p212121. a = 0.8754(2) nm, b = 1.1000(2) nm, c = 2.3117 (5) nm, V = 2.2260(8) nm3, Z=4, R(F) =0.0497.

Metalloragnische Verbindungen der Lanthanoide, 90 [1] [( tert ‐Butylcyclopentadienyl)dimethyl(tetramethylcyclopentadienyl)silan]‐Komplexe von Lanthan, Neodym und Lutetium

Organometallic Compounds of the Lanthanides, 90[1]. - [(tert-Butylcyclopentadienyl)dimethyl-(tetramethylcyclopentadienyl)silane] Complexes of Lanthanum, Neodymium, and Lutetium [(tBuC5H3)SiMe2(C5Me4)]Li2 (1) reacts with LnCl3 (Ln = La, Lu) in THF to yield [(tBuC5H3)SiMe2(C5Me4)]Ln(μ-Cl)2Li-(OEt2)2 [Ln = La (3a), Lu (3c)]. The reactions of LnCl3 (Ln = La, Nd) with [(tBuC5H3)SiMe2(C5Me4)]Na2 (2) and (C5Me4H)Na in THF result in the formation of the chiral tris(cyclopentadienyl) complexes [(tBuC5H3)SiMe2(C5Me4)]Ln-(C5Me4H)(THF) [Ln = La (4a), Nd (4b)]. The 1H- and 13CNMR and mass spectra of the new compounds as well as the X-ray crystal structure of 4a are discussed.

The exploitation of new synthetic reactions by means of rare earth metals

AbstractThis review deals with lanthanoid mediated organic reactions investigated by the authors. The scope of the lanthanoid‐mediated reactions are discussed under the following topics: Reactions of Yb metal umpoled diaryl ketones with electrophiles; Reactions of Yb metal with imines; Reactions of Yb metal with CC multiple bonds; Reactions of Sm metal with nitroarenes; Reactions of Yb metal with α,β‐unsaturated carbonyl compounds; Reactions of a PhYbI σ‐complex; Reactions of LnCl3 as Friedel‐Crafts catalyst.