Ether Complexes Research Articles

Atomistic Investigation of Crown Ether Complexes with Lithium Iodide as Solid-State Electrolytes

Abstract We investigated the surprising ionic conductivity trend of a series of hybrid complexes based on lithium iodide (LiI) associated with different size of crown ethers. Through a combination of experimental and theoretical methods, LiI hybrid complexes were characterized to rationalize the unexpected tendency of ionic conductivity. Our findings revealed that the solvation structure of the lithium iodide (LiI) complex of crown ethers is influenced by the size of the crown ether. Consequently, the solvation structure of the complex affects the transport properties. Notably, we observed a unique sandwich-like complex is formed between two 12C4 molecules and the Li cation during classical NVT molecular dynamics (MD) simulation, which is rarely observed with larger crown ethers. Based on this observation, we postulate that the idiosyncratic structure of [Li ⸦ 12C4][I] increases the ratio of SSIP solvation structure, ultimately resulting in higher ionic conductivity compared to [Li ⸦ 15C5][I], despite 15C5 is a larger crown ether than 12C4. We also propose a hypothesis, based on the MD simulation, that adjusting the size of crown ether molecules can potentially enhance the transference number.

Anionic modulation induces molecular polarity in a three-component crown ether system.

Three-component crown ether phase change materials are characterized by a structural phase change in response to external stimuli such as temperature and electric or magnetic fields, resulting in significant changes in physical properties. In this work, we designed and synthesized two novel host-guest crown ether molecules [(PTFMA)(15-crown-5)ClO4] (1) and [(PTFMA)(15-crown-5)PF6] (2), through the reaction of p-trifluoromethylaniline (PTFMA) with 15-crown-5 in perchloric acid or hexafluorophosphoric acid aqueous solution. Compound 1 undergoes a structural change from the non-centrosymmetric space group (P21) to the centrosymmetric space group (P21/c) with increasing temperature. This transformation is accompanied by a switchable second harmonic generation (SHG) signal, a noticeable dielectric response, and a reversible phase transition in differential scanning calorimetry (DSC). For compound 2, there are reversible phase transitions accompanied by a dielectric response, but it does not exhibit a switchable SHG signal. The difference in properties between the two compounds may be due to the polarity modulation of the anion, providing new ideas for obtaining crown ether complexes with SHG response properties.

Dichlorido(crown ether)lanthanoid(III) tetrachloroaluminate complexes

Reactions between LnCl3, AlCl3 and a crown ether (18-crown-6 and dibenzo18-crown-6) in MeCN have led to the isolation of four new lanthanoid halide crown ether complexes, [PrCl(μ-Cl)(18-crown-6)]2[AlCl4]2·2MeCN (1), [YbCl2(18-crown-6)][AlCl4]·MeCN (2), and [LnCl(μ-Cl)(dibenzo18-crown-6)}2][AlCl4]2·6.5MeCN (Ln = La, 3, Pr, 4). 1 was also obtained by unexpected halide transfer on addition of 18-crown-6 (18C6) to MeCN solutions of [Pr(MeCN)9][AlCl4]3. Complexes 1, 3 and 4 have dinuclear chloride-bridged nine-coordinate cations, and 2 has an eight coordinate mononuclear cation.

Fluorimetric methods for determination of aluminum in water resources utilizing newly synthesized N,N'-bis(2,5-dihydroxybenzylidene)-4,4′-diamino diphenyl ether

Industrial waste contaimnation of water sources is a serious environmental problem. As a result, it's critical to identify metallic contamination in water with precision, sensitivity, and accuracy. In acetonitrile, the fluorimetric parameters of N,N-'bis(2,5-dihydroxybenzylidene)-4,4′-diamino diphenyl ether (DHDPE) and aluminum complex were determined. In the acetonitrile medium, the best fluorescence intensity of the DHDPE-Al complex was observed at λex = 280 nm, λem = 391 nm (excitation and emission wavelengths). For optimum complex formation, the ideal pH, duration, and temperature were 4.5, 20 min, and 25 °C, respectively. Within the ranges of 0.027–0.27 and 0.27–2.70 ppm aluminum concentrations, [Al3+]-F.I. Calibration graphs were linear. The fluorimetric aluminum measurement method was applied to diverse water sources using the newly synthesized macro molecular Schiff base DHDPE as the ligand. The aluminum concentration in water inflow to KOSKI (Konya Water and Sewerage Administration) was doubled as a result of the examination when compared to other samples of water.

Thermal Formation of Metathesis-Active Tungsten Alkylidene Complexes from Cyclohexene.

A 7-tungstabicyclo[4.3.0]nonane complex forms slowly upon addition of cyclohexene to the ethylene complex, W(NAr)(OSiPh3)2(C2H4), at 22 °C. A single-crystal X-ray study showed its structure to be closest to a square pyramid (τ = 0.23). At 22 °C, loss of cyclohexene or ring contraction of the 7-tungstabicyclo[4.3.0]nonane complex is slow. Above ∼80 °C, cyclohexene is ejected to give W(NAr)(OSiPh3)2(C2H4), but a sufficient amount of 7-tungstabicyclo[4.3.0]nonane complex remains in the presence of cyclohexene and the ring contracts to yield methylenecyclohexane and a methylidene complex or ethylene and a cyclohexylidene complex. Other complexes that have been observed include an 8-tungstabicyclo[4.3.0]nonane complex formed from 1,7-octadiene, a 7-tungstabicyclo[4.2.0]octane complex (formed from a methylidene complex and cyclohexene), and a methylenecyclohexane complex. 13C-Labeling studies show that the exo-methylene group in methylenecyclohexane and the α positions in the 8-tungstabicyclo[4.3.0]nonane come from ethylene. An alternative ring contraction of a tungstacyclopentane made from two molecules of cyclohexene cannot be excluded when concentrations of ethylene are low. A cyclohexylidene complex could also form from two cyclohexenes via a newly proposed "alkyl/allyl" mechanism. The results reported here are the first experimental confirmations that a tungstacyclopentane can ring-contract thermally at a substituted WCα position to form a tungstacyclobutane and therefore metathesis-active alkylidenes.

Catalytic synthesis of flavanone without stirring or heating

We developed a new approach for the synthesis of flavanone from chalcones without electrical energy, such as stirring or heating, by using a cesium fluoride–crown ether complex. This “zero electrical energy reaction” is a new category of reaction that has the potential to replace the general organic reaction.

Ethylene Polymerizations Catalyzed by Fluorinated "Sandwich" Diimine-Nickel and Palladium Complexes.

Nickel and palladium complexes bearing "sandwich" diimine ligands with perfluorinated aryl caps have been synthesized, characterized, and explored in ethylene polymerization reactions. The X-ray crystallographic analysis of the precatalysts 16 and 6b shows differences from their nonfluorinated analogues 17 and 19, with the perfluorinated aryl caps centered precisely over the nickel and palladium centers, which results in higher buried volumes of the metal centers relative to the nonfluorinated analogues. The sandwich diimine-palladium complexes 5a and 5b containing perfluorinated aryl caps polymerize ethylene in a controlled fashion with activities that are substantially increased compared with their nonfluorinated analogues. Migratory insertion rates in relevant methyl ethylene complexes agree with the activities exhibited in bulk polymerization experiments. DFT studies suggest that facility of ethylene rotation from its preferred orientation perpendicular to the Pd-alkyl bond into a parallel in-plane conformation contributes to the higher polymerization activity for 5b relative to 18a. For these palladium systems, polymer molecular weights can be controlled via hydrogen addition (hydrogenolysis), which is unusual for late-transition-metal-catalyzed olefin polymerizations with no catalyst deactivation occurring. Sandwich diimine-nickel complexes 6a and 6b with perfluorinated aryl caps show ethylene polymerization activities that are about half of those of classical tetraisopropyl-substituted catalyst 2 but again are more active than the analogous nonfluorinated sandwich complexes. Ethylene polymerizations exhibit living behavior, and branched ultrahigh-molecular-weight polyethylenes (UHMWPEs) with very low-molecular-weight distributions (less than 1.1) are obtained. The activated nickel catalysts are stable in the absence of monomer and show good long-term stability at 25 °C.

Blue- and Red-Shifting C-H⋯O Hydrogen Bonds of Cyclic Ethers with Haloforms: Effect of Ring-Size and Consistency with Bent's Rule.

A DFT-based computational study is carried out to delve into the interplay between hyperconjugation and rehybridization effects underlying the formation of blue- or red-shifting H-bonds (HBs) in 1 : 1 complexes of cyclic ethers (HB acceptor) of varying ring-size with haloforms, CHF3 and CHCl3 (HB donor). The calculations reveal that with decreasing angular strain (increasing ring-size) of the cyclic ethers, the extent of blue-shift increases for 1 : 1 complexes with CHF3, while a reverse sequence is observed with CHCl3, eventually leading to a red-shifting HB in the oxepane : CHCl3 complex. It is noted that the trend in the shift of C-H stretching fundamental is not mirrored by the C-H bond length or interaction energies for both the systems studied, that is, the low sensitivity of the changes on the strain on the O-atom of HB acceptor (cyclic ethers) is to be emphasized.

Synthesis of cationic lanthanoid tetraphenylborate crown ether complexes

The efficacy of Me3NHBPh4 as a protolytic agent in the generation of reactive lanthanoid cations has been further explored. Reaction of [Nd(BH4)3(thf)4] with Me3NHBPh4 in a 1:3 mole ratio, and dibenzo-18-crown-6 (DB18C6) in thf did not yield [Nd(thf)n][BPh4]3, but [Nd(BH4)2(DB18C6)][BPh4]⋅2THF (1), a complex primed for further functionalisation, was isolated. The structure has an eight coordinate Nd atom with two trans tridentate BH4− ligands. Redox transmetallation/protolysis (RTP) reactions between Yb metal, PhHgC6F5, and Me3NHBPh4 in the presence of 18-crown-6 (18C6) or DB18C6 in MeCN or in thf followed by work up with MeCN yields [Yb(CE)(MeCN)3][BPh4]2⋅nMeCN (CE = 18C6, n = 0 (2), and DB18C6 n = 3 (3)), the structures of which have nine coordinate Yb atoms. Two pairs of MeCN ligands are transoid, whereas the third pair have a small cis NYbN angle. In the absence of a crown ether ligand, the RTP reaction in MeCN yields the known [Yb(MeCN)8] [BPh4]2.

Sino-Saudi partnership lets contracts for Chinese ethylene and catalytic distillation complex

Sino-Saudi partnership lets contracts for Chinese ethylene and catalytic distillation complex

Synthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes.

Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO22+. Here, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO22+ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E1/2) of -0.18 V vs Fc+/0 upon complexation, representing the most positive UVI/UV potential yet reported for the UO2n+ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U-Ooxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.

Strong dependence of air stability on thickness in n-doped carbon nanotube thermoelectrics

We demonstrate that the observed (in-)stability of n-doped carbon nanotube films in air not only depends on the employed dopant but is also strongly affected by sample-specific factors, such as the film thickness and density. We show this for two typical dopants, polyethylenimine and a potassium crown ether complex, by preparing films of increasing thickness. We argue that reports on dopant stability cannot be properly assessed without knowledge of these sample-specific parameters, which explains some of the conflicting results in the literature.

Acid‐Free Intermolecular Hydroarylation of Acetylene Catalyzed by Dicationic Palladium(II) and Platinum(II) Ethylene Complexes

AbstractFour dicationic palladium and platinum ethylene complexes of the type [M(PNP)(C2H4)]X2 (M=Pd, Pt; X=BF4, SbF6, PNP=2,6‐bis(diphenylphosphinomethyl)pyridine) were studied as pre‐catalysts for the intermolecular hydroarylation of acetylene under acid‐free conditions. The palladium complex [Pd(PNP)(C2H4)](SbF6)2 was found to be the most active catalyst for the addition of pentamethylbenzene to acetylene at room temperature. In a 31P NMR spectroscopic study the impact of the counter anion on the rate determining step was demonstrated. Various reaction parameters were screened to optimize the catalytic efficiency. The presence of small amounts of water were beneficial and increased the reaction rate. Water acts as co‐catalyst assisting in proton transfer during the catalytic reaction. After optimization of the reaction conditions, a benchmark for the palladium(II) catalyzed hydroarylation of acetylene was achieved with TON 200 at room temperature in 24 h under acid‐free conditions. However, this catalytic system has a very limited substrate scope.

Bis-Alkoxide Dysprosium(III) Crown Ether Complexes Exhibit Tunable Air Stability and Record Energy Barrier.

High-performance and air-stable single-molecule magnets (SMMs) can offer great convenience for the fabrication of information storage devices. However, the controversial requisition of high stability and magnetic axiality is hard to balance for lanthanide-based SMMs. Here, a family of dysprosium(III) crown ether complexes possessing hexagonal-bipyramidal (pseudo-D6h symmetry) local coordination geometry with tunable air stability and effective energy barrier for magnetization reversal (Ueff) are shown. The three complexes share the common formula of [Dy(18-C-6)L2][I3] (18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane; L = I, 1; L = OtBu 2 and L = 1-AdO 3). 1 is highly unstable in the air. 2 can survive in the air for a few minutes, while 3 remains unchanged in the air for more than 1 week. This is roughly in accordance with the percentage of buried volumes of the axial ligands. More strikingly, 2 and 3 show progressive enhancement of Ueff and 3 exhibits a record high Ueff of 2427(19) K, which significantly contributes to the 100 s blocking temperature up to 11 K for Yttrium-diluted sample, setting a new benchmark for solid-state air-stable SMMs.

Rapid Quantification of Ammonium Nitrate and Urea Nitrate Using Liquid Chromatography-High-Resolution Orbitrap Mass Spectrometry.

Resolution and sensitivity improvements in mass spectrometry technology have enabled renewed attempts at solving challenging analytical issues. One such issue involves the analysis of energetic ionic species. Energetic ionic species make up an important class of chemical materials, and a more robust and versatile analytical platform would provide tremendous value to the analytical community. Initial attempts at quantification of energetic ionic species employed high-resolution time-of-flight measurements with crown ether (CE) complexation and flow injection analysis (FIA). In this investigation, ammonium nitrate (AN) and urea nitrate (UN) in the presence of a crown ether complexation agent were explored by using high-resolution orbitrap mass spectrometry. Product ion scans of these signature complexes reveal positive identification of these energetic ionic species. Finally, quantification was demonstrated for both flow injection and liquid chromatography-mass spectrometry (LC-MS) analysis, suggesting the capability for routine and rapid analysis of these energetic ionic materials.

Syntheses and Characterization of Ti(III)/Ti(IV) Triazenido Complexes

AbstractThe syntheses of side‐on Ti(III) triazenido complexes via the ethylene complexes Cp*Ti(η2‐C2H4)(η5‐C5H4CR2H) and side‐on Ti(IV) triazenido complexes via bis(π‐η5 : σ‐η1‐pentafulvene) titanium complexes are reported. The deprotonation of the triazene N−H function occurs under mild conditions either by reduction of the proton to hydrogen mediated via the masked titanocene (II) of the ethylene complex or by the nucleophilic Cexo atom of the pentafulvene moiety. The structures of the paramagnetic Ti(III) complexes were confirmed by single‐crystal X‐ray diffraction, whereas the diamagnetic Ti(IV) complexes were characterized via NMR spectroscopy and additionally, Ti2 c by single‐crystal X‐ray diffraction. The structure of complex Ti2 c reveals one of the smallest bent angles known for titanium pentafulvene complexes.

КИНЕТИЧЕСКИЙ АНАЛИЗ ТЕХНОЛОГИЧЕСКИХ КРИТЕРИЕВ ЭФФЕКТИВНОСТИ ПРОЦЕССА ОКИСЛЕНИЯ ЭТИЛБЕНЗОЛА В ПРИСУТСТВИИ КОМПЛЕКСОВ ДИБЕНЗО-18-КРАУН-6 ЭФИРА С ХЛОРИДАМИ CA, SR, BA

A kinetic scheme is proposed that is common to the processes of ethylbenzene oxidation and ethylbenzene hydroperoxide decomposition in the presence of dibenzo-18-crown-6 ether complexes with Ca, Sr, and Ba chlorides. The scheme includes reactions of the formation of intermediate adducts from components of the reaction mixture and catalyst molecules, classical reactions of initiation, propagation and termination of the chain, reactions of initiation and propagation of the chain with the participation of intermediate adducts, and molecular reactions (includingthose with the participation of intermediate adducts).Basedonexperimentaldataandtheproposedscheme, akineticmodelwasmade.The kinetic model, written in the form of nonlinear differential equations according to the mass action law describes in time the rate of change of the concentrations of all components of reaction mixtures for ethylbenzene oxidation and ethylbenzene hydroperoxide decomposition in the presence of dibenzo-18-crown-6 ether complexes with Ca, Sr, Ba chlorides. As a result of solving the inverse kinetic problem using the zero-order direct search method, the values of reaction rate coefficients were found where the kinetic model reproduces the experimental values of the concentrations of all components of the reaction mixtures of the processes under consideration within the average relative error of 25%.As a result of the analysis based on the kinetic model, it was established that the conversion of ethylbenzene in the process of its oxidation is most affected by the reaction of ethylbenzene with the ethylbenzene peroxyl radical (target reaction).Using the kinetic model, the following was shown: 1) the values of the conversion of ethylbenzene, depending on the nature of the catalyst, line up in a row that corresponds to a number of values of the reaction rates of ethylbenzene with ethylbenzene peroxyl radical; 2) the model qualitatively reproduces the trend of selectivity changes when changing the catalyst.

Going for gold - the chemistry of structurally authenticated gold(I)-ethylene complexes.

Gold coordination chemistry and catalysis involving unsaturated hydrocarbons such as olefins have experienced a remarkable growth during the last few decades. Despite the importance, isolable and well-characterized molecules with ethylene, the simplest and the most widely produced olefin, on gold are still limited. This review aims to cover features of, and strategies utilized to stabilize, gold-ethylene complexes and their diverse use in chemical transformations and homogeneous catalytic processes. Isolable and well-authenticated gold-ethylene complexes are important not only for structural, spectroscopic, and bonding studies but also as models for likely intermediates in gold mediated reactions of alkenes and gold-alkene species observed in the gas phase. There has also been development on AuI/III catalytic cycles. Nitrogen based ligands have been the most widely utilized ligand supports thus far for the successful stabilization of gold-ethylene adducts. Gold has a bright future in olefin chemistry and with ethylene.

Coinage metal-ethylene complexes of sterically demanding 1,10-phenanthroline ligands.

Phenanthroline-based ligands with bulky aryl groups flanking the metal binding pocket enabled the synthesis and detailed investigation of ethylene complexes of copper(I), silver(I), and gold(I), including structural data of [{2,9-bis(2,4,6-triisopropylphenyl)-1,10-phenanthroline}M(C2H4)][SbF6] (M = Cu, Ag, Au), Additionally, a related copper(I)-ethylene complex with a highly fluorinated ligand is also reported. Gold(I) affects the ethylene moiety significantly as evident from the notable upfield coordination shifts of ethylene carbon signals in the NMR and lengthening of the ethylene CC bond length. Silver(I) forms the weakest bond with ethylene in this series of isoleptic, group 11 metal-ethylene complexes. Preliminary catalytic investigations underscore the potential of copper complexes, particularly those with weakly coordinating supporting ligands, as effective catalysts for C(sp3)-H functionalization through trifluoromethyl carbene insertion.

Rare-earth metal ethylene and ethyne complexes

An unprecedented rare-earth ethyne complex is presented, and the α-H abstraction and C–C σ bond metathesis mechanism is proposed based on DFT calculations. The first example of a well-defined non-Cp rare-earth ethylene complex via the β-H abstraction reaction is also described herein.