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A polar copper-Boron One-Electron sigma-bond

Virtually all chemical bonds consist of one or several pairs of electrons shared by two atoms. Examples of sigma-bonds made of a single electron delocalized over two neighboring atoms were until recently found only in gas-phase cations such as H2+ and Li2 + and in highly unstable species generated in solid matrices. Only in the past decade was bona fide one-electron bonding observed for molecules in fluid solution. Here we report the isolation and structural characterization of a thermally stable compound featuring a Cu-B one-electron bond, as well as its oxidized (nonbonded) and reduced (two-electrons-bonded) congeners. This triad provides an excellent opportunity to study the degree of sigma-bonding in a metalloboratrane as a function of electron count.

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O -ylide and pi-complex formation in reactions of a carbene with dibenzo and monobenzo crown ethers

Reactions of p-nitrophenylchlorocarbene (PNPCC) with various dibenzo crown ethers produce O-ylides and pi-complexes; the reactions can be followed via the spectral signatures of the carbene and the products. The O-ylides form most rapidly, but over time they decay in favor of the more stable pi-complexes. Extensive computational studies support and refine appropriate structural and mechanistic conjectures. Reactions of PNPCC with monobenzo crown ethers afford only the spectral signatures of O-ylides; monobenzo pi-complexes are either not formed in significant concentrations or are spectroscopically silent.

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Synthesis, crystal structure and electrochemical properties of a new adduct of Benzo-15-crown-5 and H3PMo12O40

A new crown ether-POM (POM = polyoxometalate) adduct with the molecular formula [(C14-H20O5)4(H 3O)3]PMo12O40 ¡¤0.5CH 3CN (1) was isolated from the mixed solvent of acetonitrile and methanol. The adduct is constructed from Keggin [PMo12O 40]3- anions and [(C14H20O 5)-(H3O+)] and [(C14H 20O5)2(H3O+)] cations via electrostatic and hydrogen bonding interactions. The supramolecular interactions combine the crown ether with oxonium ions. In the [(C 14H20O5)-(H3O+)] moieties, the oxonium ions reside out of the planes defined by the oxygen atoms of the crown ether. The [(C14H20O5) 2(H3O+)] moieties exhibit a sandwich structure. There exist hydrogen bonds between the oxonium ions of the [(C 14H20O5)(H3O)]+ cations and the acetonitrile molecules and the terminal and bridging oxygen atoms of the [PMo12O40]3- anions. The adduct has been used as a bulk-modifier to fabricate a chemically modified carbon paste electrode (MCPE), which displays well-defined cyclic voltammograms with three reversible two-electron redox couples in acidic aqueous solution, and electrocatalytic activities towards the reduction of H2O2 and NO 2-.

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New Applications of Crown Ethers. Part 6. Stuctural Effects of Bis(benzocrown ether)s and Substituted Benzocrown Ethers on Solvent Extraction and Complexation of Alkali-metal Cations

Bis(benzocrown ether)s consisting of benzo-15-crown-5 (B15C5), benzo-18-crown-6 (B18C6) and/or benzo-21-crown-7 (B21C7) with the following linking chains, -(CH2)n- (n=2 and 8), -(CH2)3-O-, -O-(CH2)6-O-, and -(O-CH2CH2)n-O- (n=2-5), were prepared and their complexation behaviour was characterized using solvent extraction of alkali-metal picrates and complexation with alkali-metal chlorides.Bis(benzocrown ether)s were distinguished from the corresponding mono(benzocrown ether)s by their remarkable high extraction ability of a cation larger than the hole size of a crown unit, the so-called ‘biscrown effect’.Bis(B15C)s (4a-h) and bis(B18C6)s (5a-h) preferentially extracted K+ and Cs+, respectively.Bis(benzocrown ether)s containing the B21C7 unit (6a)-(8a) did not show this ‘biscrown effect’ because of the large hole size of B21C7.An unsymmetrical bis(crown ether) (7b) consisting of B15C5 and B18C6 selectively extracted Rb+.The ‘biscrown effect’ was favourably exerted with the oligoethyleneglycol linkage rather than the hydrocarbon one.Little or no effect of lipophilic groups or donor oxygens in the side chain of mono(benzocrown ether)s was observed in the extraction of alkali-metal picrates.Stability constants were determined by the ionselective electrode method in 90percent methanol aqueous solution at 25 deg C.In bis(B15C5)s with Na+, and bis(B18C6)s with Na+ or K+, two crown rings in one molecule acted as two individual moieties.Bis(B15C5)s bound with K+ to form preferentially an intramolecular 2:1 crown ether unit-K+ complex.Both bis(B15C5)s with Cs+ and bis(B18C6)s with Cs+ systems also showed the ‘biscrown effect’.

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Optimization of lithium separation conditions from Caspian seawater using fuzzy logic combined with dispersive liquid?liquid extraction

For optimization of separation conditions of lithium from the Caspian seawater, a new combination technique of liquid?liquid extraction and fuzzy logic is being used. In this research, disperser and extraction solvents, and ligand of benzo15-crown-5, have been quickly injected. It went to cloudy form solution contain small extraction solvent drops. The impact of different parameters such as the kind and concentration of benzo15-crown-5, the volume of disperser and extraction solvents, pH and extraction time have been optimized on the extraction percentage and analyzed using fuzzy logic. The effect of other metal ion on extraction percentage was also investigated. Under the optimized conditions (volume of tetrachloroethylene: 1.5 mL, volume of acetone: 120 mL, volume of benzo15-crown-5: 0.1 mL, concentration of benzo15-crown-5: 0.001?mol/L, and pH: 1), the extraction has increased to 74% for the synthesis sample and 31% for the real sample from Caspian seawater.

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Recent progress of organic and hybrid thermoelectric materials

Organic and hybrid thermoelectric materials have been very rapidly developed in the past decade, because the requirement for new energy and energy savings has increased due to the rapid economic development of developing countries and environmental crisis resulting in global warming. Thermoelectric technology has been considered to create electricity from a temperature difference, and be effective for energy harvesting. Organic and hybrid thermoelectric materials cannot be used at high temperature. In the practical world, most of the waste heat energy comes from temperatures below 150?C. Thus, organic materials could be applied to recover electricity from waste heat energy below 150?C. In this review, after an introduction of the advantages of organic and hybrid thermoelectric materials, their brief history over two decades and the recent progress to improve the thermoelectric performance will be described by focusing on the researches of the author’s group.

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Benzo- and dibenzo-crown ethers substituted with (azulene-1-yl) azo chromophores. Synthesis and properties

Colored benzo- and dibenzo-crown ethers with (azulene-1-yl) azo chromophores(s) at benzo ring(s) were synthesized in good yields starting from the amines of the benzo- and dibenzo-crown ethers which were diazotized and coupled with azulenes. The obtained crown ethers were characterized and several properties of the generated new dyes were investigated (electronic and NMR-spectra, as well as pKa values, the lipophilicity and the coordination with metal cations).

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Ion-pair extraction of uranyl ion from aqueous medium using crown ethers

Ion-pair extraction behaviour of uranyl ion from aqueous solutions was studied at pH 3.0 employing crown ethers viz. benzo 15 crown 5 (B15C5), 18 crown 6 (18C6), dibenzo 18 crown 6 (DB18C6), and dibenzo 24 crown 8 (DB24C8) in chloroform as the organic phase and picric acid as the organophilic counter anion. The stoichiometry of the extracted species corresponded to [UO2(crown ether)(n)]2+ ¡¤[pic-]2 where n = 1.5 for benzo 15 crown 5 and 1 for 18 crown 6 as well as dibenzo 18 crown 6. Adducts of DB24C8 could not be observed as practically no extraction was possible using this reagent. The separation behaviour of fission products from an irradiated uranium target was also studied. An interesting observation on the separation of trivalent lanthanides from uranyl ion is reported.

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Structure and Reactivity of Lithium and Sodium Aryloxides in Dimethylformamide. Ions, Ion Pairs, and Ion Triplets

Reactivity and u.v. spectra of aryloxide ions in dimethylformamide are affected by the addition of either Li(1+) and Na(1+) ions in a way that suggests the occurrence of ion triplets M(1+)A(1-)M(1+) in addition to free ions and ion pairs.

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Ruthenium-benzocrownether complexes: Synthesis, structures, catalysis and immobilisation in ionic liquids

A facile pathway to [RuCl2(eta6-benzocrownether)] 2 complexes is described and crystal structures of the complexes [RuCl2(eta6-benzo-15-crown-5)]2 and [RuCl2(eta6-dibenzo-18-crown-6)]2 are reported. The complexes were derivatised with (1S,2R)-2-amino-1,2- diphenylethanol and evaluated in the enantioselective transfer-hydrogenation of acetophenone. The effect of complexation of different alkaline metals (Na, K, Cs) within the crown on the selectivity and reaction rate was studied. Interaction of a sulfonated phosphine ligand with the crown was probed by NOESY-NMR and utilisation of the crownether to serve as an anchor for catalyst immobilisation was investigated.

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