Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes.

LnCl(THF) (Ln = Y, La ÷ Nd, Sm ÷ Lu) readily react with the tridentate 1,3,5-trimethyl-1,3,5-triazacyclohexane (Metach) ligand to form mono- or binuclear lanthanide trichloride complexes, depending on the stoichiometry of the reaction and the ionic radius of the metal: mononuclear pseudosandwich [LnCl(Metach)], (Ln = Y, La ÷ Ho) or binuclear complexes [LnCl(Metach)], or [LnCl(Metach)(THF)] (Ln = Sm, Tb). Detailed analysis of the NMR data of [LnCl(Metach)] complexes with paramagnetic lanthanide ions showed that their structures remained unchanged in the toluene solution. A series of isomorphous complexes [LnCl(Metach)(Py)] (Ln = La, Sm, Tb, Er, Lu; Py = pyridine) have been obtained by the recrystallization of either mononuclear or binuclear complexes from pyridine.

Coordination Polymers of Polyphenyl-Substituted Potassium Cyclopentadienides.

A series of potassium salts of di- and tri-arylsubstituted cyclopentadienes has been obtained by the metalation of the corresponding cyclopentadienes with benzylpotassium in THF media. Crystals of all compounds, afforded by recrystallization from THF/hexane, diglyme-THF/hexane and toluene/hexane mixtures, have been studied by X-ray diffraction. All studied potassium cyclopentadienides exhibit the luminescence at room temperature and overall quantum yield of photoluminescence for potassium salt of diarylsubstituted cyclopentadiene is 18%.

Bis(η-cyclo-penta-dien-yl)(2-{[(2-meth-oxy-phen-yl)imino]-meth-yl}phenolato-κ ,,')terbium.

The air- and moisture-sensitive title compound, [Tb(CH)(CHNO)], was synthesized from tris-(cyclo-penta-dien-yl)(tetra-hydro-furan)-terbium and 2-{[(2-meth-oxy-phen-yl)imino]-meth-yl}phenol. Each Tb atom is coordinated by two cyclo-penta-dienyl ligands in an η-coordination mode and by one N and two O atoms of the organic ligand in a tridentate κ ,,'-mode.

Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes.

Organophosphate-chloride complexes [{(2,6-PrCH-O)POO}LnCl(CHOH)]·2CHOH, Ln = Nd (), Eu (), Gd (), and Tb () have been obtained and structurally characterized. Their reaction with 2,2':6',2″-terpyridine leads to the formation of 1:1 adducts ([{(2,6-PrCH-O)POO}LnCl(terpy)(HO)(CHOH)], Ln = Eu (), Gd (), Tb () with exception of Nd, where tris-diisopropylphenylphosphate complex [{(2,6-PrCH-O)POO}Nd) (terpy)(HO)(CHOH)] () was obtained due to the ligand metathesis. A bright luminescence observed for the Eu and Tb organophosphate complexes is the first example of an application of organophosphate ligands for 4f-ions luminescence sensitization.

Crystal structure of tris-[bis-(2,6-diiso-propyl-phen-yl) phosphato-κ]penta-kis-(methanol-κ)europium methanol monosolvate.

The mononuclear title complex, [Eu(CHOP)(CHO)]·CHO, (), has been obtained as a minor product in the reaction between EuCl(HO) and lithium bis-(2,6-diiso-propyl-phen-yl) phosphate in a 1:3 molar ratio in a methanol medium. Its structure exhibits monoclinic (2/) symmetry at 120 K and is isostructural with the La, Ce and Nd analogs reported previously [Minyaev (2018 ▸). C, 590-598].

(1,2,4)-1,2,4-Tri-phenyl-cyclo-pentane-1,2-diol and (1,2,4)-4-(2-meth-oxy-phen-yl)-1,2-di-phenyl-cyclo-pentane-1,2-diol: application as initiators for ring-opening polymerization of ∊-caprolactone.

Reductive cyclization of 1,3,5-triphenyl- and 3-(2-meth-oxy-phen-yl)-1,5-di-phenyl-pentane-1,5-diones by zinc in acetic acid medium leads to the formation of 1,2,4-tri-phenyl-cyclo-pentane-1,2-diol [1,2,4-PhCH-1,2-(OH), CHO, ()] and 4-(2-meth-oxy-phen-yl)-1,2-di-phenyl-cyclo-pentane-1,2-diol [4-(2-MeOCH)-1,2-PhCH-1,2-(OH), CHO, ()]. Their single crystals have been obtained by crystallization from a THF/hexane solvent mixture. Diols () and () crystallize in ortho-rhom-bic () and triclinic ( ) space groups, respectively, at 150 K.

Bis[μ-bis-(2,6-diiso-propyl-phen-yl) phosphato-κ :']bis-[(2,2'-bi-pyridine-κ ,')lithium] toluene disolvate and its catalytic activity in ring-opening polymerization of ∊-caprolactone and l-dilactide.

The solvated centrosymmmtric title compound, [Li(CHOP)(CHN)]·2CH, was formed in the reaction between {Li[(2,6-PrCH-O)POO](MeOH)}(MeOH) and 2,2'-bi-pyridine (bipy) in toluene. The structure has monoclinic (2/) symmetry at 120 K and the asymmetric unit consists of half a complex mol-ecule and one mol-ecule of toluene solvent. The diaryl phosphate ligand demonstrates a μ-κ:κ'-bridging coordination mode and the 2,2'-bi-pyridine ligand is chelating to the Li cation, generating a distorted tetra-hedral LiNO coordination polyhedron.

Crystal structure of bis-(μ-meth-anolato-κ:κ)hexa-methyl-bis-(μ-tri-phenyl-acetato-κ:κ')bis-(μ-tri-phenyl-acetato-κ ,':κ)dialuminiumdi-lanthanum toluene tetra-solvate.

The title compound, [AlLa(CHO)(CH)(CHO)]·4CHCH or [{La(PhCCOO)(MeAlOMe)}]·4CHCH, was formed in a reaction between lanthanum tris-(tetra-methyl-aluminate) and tri-phenyl-acetic acid (1:1) with unintended partial oxidation. The tri-phenyl-acetate ligand exhibits μ-κ :κ ' bridging and μ-κ ,':κ semi-bridging coordination modes, forming a dimeric La(μ-OCO) core. The semi-bridging tri-phenyl-acetate group provides additional bonding with an La cation the π-system of one of its phenyl rings.

Different coordination modes of trans-2-{[(2-methoxyphenyl)imino]methyl}phenoxide in rare-earth complexes: influence of the metal cation radius and the number of ligands on steric congestion and ligand coordination modes.

A simple and effective synthetic route to homo- and heteroleptic rare-earth (Ln = Y, La and Nd) complexes with a tridentate Schiff base anion has been demonstrated using exchange reactions of rare-earth chlorides with in-situ-generated sodium (E)-2-{[(2-methoxyphenyl)imino]methyl}phenoxide in different molar ratios in absolute methanol. Five crystal structures have been determined and studied, namely tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-κO,N,O)lanthanum, [La(CHNO)], (1), tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-κO,N,O)neodymium tetrahydrofuran disolvate, [La(CHNO)]·2CHO, (2)·2THF, tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-κO,N,O;κO,N,O;κN,O-yttrium, [Y(CHNO)], (3), dichlorido-1κCl,2κCl-μ-methanolato-1:2κO:O-methanol-2κO-(μ-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1κO,N,O:2κO)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-1κO,N,O;2κO,N,O-diyttrium-tetrahydrofuran-methanol (1/1/1), [Y(CHNO)(CHO)Cl(CHO)]·CHO·CHO, (4)·MeOH·THF, and bis(μ-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1κO,N,O:2κO)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato-2κO,N,O)sodiumyttrium chloroform disolvate, [NaY(CHNO)]·2CHCl, (5)·2CHCl. Structural peculiarities of homoleptic tris(iminophenoxide)s (1)-(3), binuclear tris(iminophenoxide) (4) and homoleptic ate tetrakis(iminophenoxide) (5) are discussed.

(2,3)-1,4-Dioxa-spiro-[4.4]nonane-2,3-di-carb-oxy-lic and (2,3)-1,4-dioxa-spiro-[4.5]decane-2,3-di-carb-oxy-lic acids.

The title compounds, CHO and CHO, were formed by careful hydrolysis of the corresponding diethyl esters. Their single crystals were grown from an ethyl acetate/hexane mixture. Crystals of both compounds have monoclinic (2) symmetry with a single mol-ecule in the asymmetric unit.

Polyphenylcyclopentadienyl Ligands as an Effective Light-Harvesting π-Bonded Antenna for Lanthanide +3 Ions.

A new approach to design "antenna-ligands" to enhance the photoluminescence of lanthanide coordination compounds has been developed based on a π-type ligand-the polyphenyl-substituted cyclopentadienyl. The complexes of di-, tri-, and tetraphenyl cyclopentadienyl ligands with Tb and Gd have been synthesized and all the possible structural types from mononuclear to di- and tetranuclear complexes, as well as a coordination polymer were obtained. All types of the complexes have been studied by single-crystal X-ray diffraction and optical spectroscopy.

Synthesis and characterization of an Fe(i) cage complex with high stability towards strong H-acids.

The first synthesized and X-ray structurally characterized "classical" iron(i) dioximate showed an unrivaled stability towards strong acids, thus calling for a reassessment of the origins of the electrocatalytic activity of similar low-valent cobalt and iron cage complexes with electron-withdrawing ribbed substituents, shown previously to be effective electrocatalysts of the HER.

Di- and triphenylacetate complexes of yttrium and europium.

The significant variety in the crystal structures of rare-earth carboxylate complexes is due to both the large coordination numbers of the rare-earth cations and the ability of the carboxylate anions to form several types of bridges between rare-earth metal atoms. Therefore, these complexes are represented by mono-, di- and polynuclear complexes, and by coordination polymers. The interaction of LnCl3(thf)x (Ln = Eu or Y; thf is tetrahydrofuran) with sodium or diethylammonium diphenylacetate in methanol followed by recrystallization from a DME/THF/hexane solvent mixture (DME is 1,2-dimethoxyethane) leads to crystals of the non-isomorphic dinuclear complexes tetrakis(μ-2,2-diphenylacetato)-κ(4)O:O';κ(3)O,O':O';κ(3)O:O,O'-bis[(1,2-dimethoxyethane-κ(2)O,O')(2,2-diphenylacetato-κ(2)O,O')europium(III)], [Eu(C14H11O2)6(C4H10O2)2], (I), and tetrakis(μ-2,2-diphenylacetato)-κ(4)O:O';κ(3)O,O':O';κ(3)O:O,O'-bis[(1,2-dimethoxyethane-κ(2)O,O')(2,2-diphenylacetato-κ(2)O,O')yttrium(III)], [Y(C14H11O2)6(C4H10O2)2], (II), possessing monoclinic (P21/c) symmetry.

A structural study of (1RS,2SR,3RS,4SR,5RS)-2,4-dibenzoyl-1,3,5-triphenylcyclohexan-1-ol chloroform hemisolvate and (1RS,2SR,3RS,4SR,5RS)-2,4-dibenzoyl-1-phenyl-3,5-bis(2-methoxyphenyl)cyclohexan-1-ol.

(1RS,2SR,3RS,4SR,5RS)-2,4-Dibenzoyl-1,3,5-triphenylcyclohexan-1-ol or (4-hydroxy-2,4,6-triphenylcyclohexane-1,3-diyl)bis(phenylmethanone), C38H32O3, (1), is formed as a by-product in the NaOH-catalyzed synthesis of 1,3,5-triphenylpentane-1,5-dione from acetophenone and benzaldehyde. Single crystals of the chloroform hemisolvate, C38H32O3·0.5CHCl3, were grown from chloroform.

Coordination of 2,2'-bipyridyl and 1,10-phenanthroline to yttrium and lanthanum complexes based on a scorpionate ligand.

Reaction of yttrium and lanthanum trichloride with 1 equiv of sodium or potassium hydrotris(3,5-dimethylpyrazolyl)borate and 1 equiv of 2,2'-bipyridine gives good yields of the complexes [MCl(2)(Tp(Me2))(C(10)H(8)N(2))] (M = Y (1), La (2)). The analogous compounds with 1,10-phenanthroline, [MCl(2)(Tp(Me2))(C(12)H(8)N(2))] (M = Y (3), La (4)), have been obtained by a similar procedure. The solid-state structures of 2-4 were determined by single-crystal X-ray diffraction and revealed that the compounds are all seven-coordinate with capped octahedral geometry.

Triamidotriazacyclononane complexes of group 3 metals. Synthesis and crystal structures.

Reaction of yttrium and lanthanide trichlorides (Ln = La, Eu, Yb) with 1 equiv of the trisodium salt of 1,4,7-tris(dimethylsilylaniline)-1,4,7-triazacyclononane (Na(3)[(SiMe(2)NPh)(3)-tacn](THF)(2)) gives good yields of the compounds [M[(SiMe(2)NPh)(3)-tacn]] (M = Y (1), Eu (3), Yb (4)) and [La[(SiMe(2)NPh)(3)-tacn](THF)] (2). Reduction of 3 with Na/Hg followed by recrystallization in the presence of diglyme yielded crystals of [Eu[(SiMe(2)NPh)(3)-tacn]][Na(diglyme)(2)] (5). Synthesis of the uranium(III) complex [U[(SiMe(2)NPh)(3)-tacn]] (6) is achieved by reaction of 1 equiv of Na(3)[(SiMe(2)NPh)(3)-tacn](THF)(2) with uranium triiodide.