The use of chiral (salen)TiCl2 complexes to induce the asymmetric addition trimethylsilyl cyanide aldehydes has been investigated. are catalytically active at substrate-to-catalyst ratios as high 1000:1, and optimal catalyst (2e) which is derived from (R,R)-1,2-diaminocyclohexane 3,5-di-tert-butyl-2-hydroxybenzaldehyde produces ethers cyanohydrins with up 90% enantiomeric excess ambient temperature. Water plays a key role in these reactions since under strictly anhydrous conditions much...

We found for the first time a new origin of selection perovskite crystallization pathways from DMF solutions containing MAI and PbI2 to present here comprehensive study full set essential intermediate phases determining perovskite's morphology. For all three discovered structurally different forming at given precursor ratio, we refined their crystal structures by synchrotron X-ray radiation investigated dynamics phase assemblage in course decomposition. As result, revealed clear correlation...

Metal complexes bearing N-heterocyclic carbene (NHC) ligands are typically considered the system of choice for homogeneous catalysis with well-defined molecular active species due to their stable metal–ligand framework. A detailed study involving 19 different Pd-NHC imidazolium, benzimidazolium, and triazolium has been carried out in present work revealed a new mode operation metal-NHC systems. The catalytic activity studied systems is predominantly determined by cleavage metal–NHC bond,...

This paper concisely describes capabilities of the ‘Belok’ beamline at Kurchatov synchrotron radiation source, related to high-throughput small-molecule X-ray crystallography. As case examples, a series four novel transition metal complexes with azomethine ligands were selected. The demonstrate somewhat unexpected changes in coordination geometry and nuclearity response introduction substituents ligand’s periphery.

The chemical origin of solvents typically used for preparation hybrid lead halide perovskites—dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and γ-butyrolactone (GBL)—strongly influences the process perovskite crystallization because formation intermediate adducts with different structures morphology. composition crystal depend on coordination binding ability ratio precursors. New GBL either an unusual cluster structure, (MA)8(GBL)x[Pb18I44], or adduct, (MA)2(GBL)2Pb3I8, similar to...

The mercury test is a rapid and widely used method for distinguishing truly homogeneous molecular catalysis from nanoparticle metal catalysis. In the current work, using various M0 MII complexes of palladium platinum that are often in as examples, we demonstrated generally inadequate between cluster/nanoparticle mechanisms following reasons: (i) general facile reactivity both toward metallic (ii) very high unpredictable dependence results on operational conditions inability to develop...

A series of new zinc(II)–thiophene-2,5-dicarboxylate (tdc) MOFs based on novel dodecanuclear wheel-shaped building blocks has been synthesized in almost quantative yields. Single-crystal X-ray diffraction analyses reveal 3D porous frameworks with a complex composition [Zn12(tdc)6(glycolate)6(dabco)3] where glycolate is deprotonated polyatomic alcohol (ethylene glycol, EgO2, 1; 1,2-propanediol, PrO2, 2; 1,2-butanediol, BuO2, 3; 1,2-pentanediol, PeO2, 4; glycerol, GlO2, 5) and dabco...

Abstract We propose a new concept of the triple role protic ionic liquids with nucleophilic anions: a) regenerable solvent, b) Brønsted acid inducing diverse transformations via general catalysis, and c) source nucleophile. The efficiency this strategy was demonstrated using thiocyanate‐based for ring‐opening donor‐acceptor cyclopropanes. A wide variety activated cyclopropanes were found to react 1‐methylimidazolium thiocyanate under mild metal‐free conditions unusual nitrogen attack...

A novel approach was developed to prepare Pd nanoparticles with organic ligands in high yields. The structural unit of the species constructed involving Pd−S bonds. synthesized particles were highly selective catalysts S−H bond addition alkynes under microwave heating. An X-ray diffraction study one products reaction revealed unusual supramolecular organization cation/anion layers.

An unprecedented sustainable procedure was developed to produce functionalized vinyl monomers H(2)C═C(R)(FG) starting from a mixture of sulfur and selenium compounds as functional group donor (FG = S or Se). The reaction serves model for efficient utilization natural resources feedstock in oil technological sources sulfur/selenium. catalytic system is reported with amazing ability recognize SH/SeH groups the selectively incorporate them into valuable organic products via wastes-free...

A series of new 6- and 7-membered N-heterocyclic carbene (NHC) complexes palladium (NHC)Pd(cinn)Cl (cinn = cinnamyl 3-phenylallyl) were synthesized characterized structurally in the solid state. The influence ring size (5, 6 or 7) bulkiness N-aryl substituents (Mes 2,4,6-trimethylphenyl, Dipp 2,6-diisopropylphenyl) carbenes on catalysed Suzuki–Miyaura cross-coupling was revealed. Due to unique stereoelectronic properties expanded NHCs, a versatile, highly efficient green protocol coupling...

Three different types of drug delivery platforms based on imidazolium ionic liquids (ILs) were synthesized in high preparative yields, namely, the models involving (i) binding and IL; (ii) covalent (iii) dual using both approaches. Seven containing salicylic acid (SA-ILs) cation or/and anion prepared, their cytotoxicity toward human cell lines CaCo-2 (colorectal adenocarcinoma) 3215 LS (normal fibroblasts) was evaluated. Cytotoxicity SA-ILs significantly higher than that conventional...

Vinyl sulfides represent an important class of compounds in organic chemistry and materials science. Atom-economic addition thiols to the triple bond alkynes provides excellent opportunity for environmentally friendly processes. We have found that well-known readily available Pd-NHC complex (IMes)Pd(acac)Cl is efficient catalyst alkyne hydrothiolation. The reported technique a general one-pot approach selective preparation Markovnikov-type vinyl starting from tertiary, secondary, or primary...

Small cations such as guanidinium and cesium can act templating to form low dimensional phases (2D, 1D, 0D) in the case of excess organic halides. However, with widely used formamidinium (FA+) cation have not been reported so far. In this study, we discovered two novel a composition FA2PbBr4 investigated prerequisites their formation upon crystallization FABr-excessive solutions FAPbBr3. We found that both structure (110) layered perovskite but are represented by different polymorphs...

We report the synthesis and single-crystal X-ray diffraction, magnetic, luminescence measurements of a novel family luminescent cage-like tetranuclear silsesquioxanes (PhSiO 1.5 ) 8 (LnO 4 (O)(C 5 H O 2 6 (EtOH) (CH 3 CN) ⋅2CH CN (where Ln = Tb, 1 ; Tb/Eu, Gd, ), featuring seven-coordinated lanthanide ions arranged in one-capped trigonal prism geometry. Compounds exhibit characteristic Tb 3+ /Eu -related emissions, respectively, sensitized by chelating antenna acetylacetonate (acac) ligands...

The utility of the chiral [Ti(μ-O)(salen)]2 complexes (R)- and (S)-1 (H2salen was prepared from (R,R)- or (S,S)-cyclohexane-1,2-diamine 3,5-di(tert-butyl)-2-hydroxybenzaldehyde) as catalysts for asymmetric addition KCN Ac2O to aldehydes produce O-acetylcyanohydrins investigated. It shown that were active at a substrate/catalyst ratio 100 : 1 produced O-protected cyanohydrins with ee in range 60–92% −40°. Other complexes, [Ti2(AcO)2(μ-O)(salen)2] ((R)-4) [Ti(CF3COO)2(salen)] ((R)-5), (R)-1 by...

The synthesis, characterization, and anion-binding properties of a series 2,6-diamidopyridine dipyrromethane hybrid macrocycles is presented. As part this work, new method for effecting the oxidation dipyrromethane-based in organic solvents has been developed. macrocyclic frameworks presented here stand out because their ease synthesis tunable properties. Evidence anion binding was obtained from UV-vis spectroscopic titrations carried acetonitrile. results clearly indicate that by changing...

Three new amido-imine-type hybrid macrocycles based on substituted pyrrole units have been synthesized and shown to act as effective receptors for oxoanions in the solid state acetonitrile solution. One of question, compound 15, was characterized by X-ray diffraction analysis free macrocycle a complex with sulfuric acid. A comparison resulting structures reveals that this receptor is capable undergoing conformational change and, consequence, varying number donor sites can interact bound...

We have developed two new catalytic systems based on Ni and Pd complexes to solve the challenging problem of dialkyldichalcogenide (Alk2E2; E=S, Se) addition alkynes. A comparative study systems-Ni/PMe2Ph Pd/PCy2Ph-has revealed that catalyst is superior with respect high activity more general scope relative system. novel synthetic methodology was for preparation (Z)-bis(alkylthio)alkenes (Z)-bis(alkylseleno)alkenes from terminal alkynes excellent stereoselectivity yields.

The macrocyclic receptors 4−6 were synthesized via the anion-templated condensation of appropriately chosen dialdehyde and diamine building blocks. Whereas all three products could be obtained directly appropriate choice reaction conditions, larger [3+3] product, 6, which incorporates each precursor subunit, also conveniently an indirect procedure involving ring expansion smaller [2+2] macrocycle 4. As detailed earlier (Sessler, J. L.; Katayev, E. A.; Pantos, G. D.; Reshetova, M. Khrustalev,...

The present study reports the evidence for multiple carbon-carbon bond insertion into metal-heteroatom via a five-coordinate metal complex. Detailed analysis of model catalytic reaction carbon-sulfur (C-S) formation unveiled mechanism metal-mediated alkyne insertion: new pathway C-S without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this metal-sulfur led intermediate complex capable direct reductive elimination. In...