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Two-electron reductive carbonylation of the uranium(VI) nitride [U(TrenTIPS)(N)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(TrenTIPS)(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(TrenTIPS)] (4) and KNCO, or cyanate retention in [U(TrenTIPS)(NCO)][K(B15C5)2] (5, B15C5=benzo-15-crown-5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(TrenTIPS)(N)K}2] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(TrenTIPS)(N)][K(B15C5)2] (7). Notably, 7 reacts with CO much faster than 2. This unprecedented f-block reactivity was modeled theoretically, revealing nucleophilic attack of the pi? orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcal mol-1 for uranium(VI) and uranium(V), respectively. A remarkably simple two-step, two-electron cycle for the conversion of azide to nitride to cyanate using 4, NaN3 and CO is presented.

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Reference:
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Solid-liquid equilibria established in the presence of phase-transfer catalysts have been studied.Three types of isotherms were distinguished for complexing catalysts, and interpreted using the ratio, Ksol= dissolved anion concentration/total ligand concentration.Equilibria established in the presence of onium salts were also studied.

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Imidacloprid (IMI) derivatives conjugated with benzo-15-crown-5 and benzo-18-crown-6 structures, applied for the first time to explore novel insecticidal molecule, elicited strong excitatory toxic signs to the house flies and stunningly exhibited three to five times higher insecticidal activity than that of the parent IMI, yet the two benzo-crown structures themselves had no effect.

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Chiral Catalysts,
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Irradiation of the acetonitrile solution of 4′-(5,6-dicyanopyrazin-2-yl)benzo-15-crown-5 (1) or 4-(5,6-dicyanopyrazin-2-yl)-1,2-dimethoxybenzene (2) in the presence of triethylamine gave monodecyano-derivative (3 or 4) and bisdecyano-derivative (5 or 6).Sodium ion stimulates the reaction of the crown ether derivative.

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Chiral Catalysts,
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Recent progress in the area of molecular logic, in particular molecules capable of sensing for acidity and oxidizability, are gathered together in this short review. Originally proposed as AND logic gates that provide a high fluorescence output when simultaneously protonated and oxidized, the concept has been extended from two-input to three-input variants and to include molecules that function as INHIBIT logic gates. Photochemical concepts such as photoinduced electron transfer (PET) and internal charge transfer (ICT) are exploited as favorite design concepts. This review highlights the evolution of Pourbaix sensors with anthracene, pyrazoline, and naphthalimide fluorophores. Future applications abound in various disciplines from corrosion science, material science, geochemistry to cell imaging.

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Chiral Catalysts,
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Dibenzyldiaza- 18-crown-6 (PhCH2CH2Ph, 1), di(dodecyldiaza-18- crown-6(C12H25C12H25, 2), HOOC(CH2)11(CH2)11COOH (3), <18N>(CH2)12(CH2)12 (4), (CH2)12(CH2)12 (5), C12H25(CH2)12(CH2)12C12H25 (6), PhCH2(CH2)12(CH2)12CH2Ph(7), 4-(p- MeOC6H4CH2C12)2 (8), (p-NO2C6H4CH2C12)2 (9), and [chol-O-(CH2)2C12]2(N18N) (10) were studied. Octanol- water partition coefficients were determined for 1, 6, 7, 8, 10, and 3- cholestanyl-OCOCH2(CH2)12(CH2)12COCH2O-3- cholestanyl (11). All were found to favor octanol, and by implication the phospholipid bilayer membrane, by at least 104-fold. Transport of Na+ was assessed in both a phospholipid bilayer and in a bulk CHCl3 membrane phase. Addition of ionophores to the latter was found in some cases to strongly enhance CHCl3 phase hydration. An attempt to correlate transport rates determined in the two systems failed, suggesting that the carrier mechanism, required in the CHCl3 phase, does not apply to the tris(macrocyclic) compounds in the bilayer. Sodium transport rates were also assessed for these compounds by using the bilayer clamp technique. Although Na+ flux rates thus determined for 7-9 in the phospholipid bilayer did not correlate with results obtained by the 23Na-NMR technique, the traces are similar to those obtained with protein channels, further supporting the function of tris(macrocycle)s as channel formers.

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Reference:
Chiral Catalysts,
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The complex formation of lithium with benzo-15-crown-5 (B15C5) was investigated. The complexes LiB15C5H2OX, where X = Cl? (1), I? (2), (3), (5), and LiBF4B15C5 (4) were synthesized and studied by IR spectroscopy. Complexes 1?4 were examined by X-ray diffraction. According to IR spectroscopy data, the crown ether conformation changes upon dissolution. The interaction of the extracted complex with the solvent was identified.

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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare

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Two new ditopic receptors for alpha,omega-alkanediyldiammonium cations based on a tetraazamacrocyclic (cyclidene) nickel(II) complex bearing two crown-ether residues were synthesized. The studies of the host-guest interaction between the receptors and a series of alpha,omega-diammonium salts by NMR titration in acetonitrile-d3 showed that 1:1 complexes are formed with Kassoc?103-105M-1. Receptor 1 with benzo-15-crown-5 arms showed substantial selectivity in binding of trimethylene- and tetramethylenediammonium dications, and 1-2 orders of magnitude weaker binding of shorter (C2) or longer (C5 and C6) diammonium cations. Receptor 2 with benzo-18-crown-6 arms showed higher affinity to all studied diammonium cations, but the recognition of the length of alpha,omega-diammonium cations was less pronounced.

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Chiral Catalysts,
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Solid crown ethers and crown ether complexes with well determined crystal structures have been examined by 13C cross-polarisation magic-angle-spinning (CPMAS) n.m.r.Certain carbon atoms in most of the compounds studied gave single lines in the solution-state spectra, but produced multiplets in the spectra of solids.Such multiplicities depend on the conformation and packing adopted by the molecules in the solid state and a qualitative discussion is presented of the origins of such splittings in these compounds.The sensitivity of 13C CPMAS spectra to subtle structural differences is reflected in the differences between the spectra of two isomorphous complexes.

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Chiral Catalysts,
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For decreasing the HETP value of a column packed with a crown ether adsorbent for the separation of lithium isotopes by displacement chromatography, adsorbents were prepared using porous silica beads having diameters of 60, 100, and 250 mum and benzo-15-crown-5 ether. The HETP values of the packed column were estimated by chromatographic experiments by data obtained from breakthrough curves. The HETP values decreased with the particle diameter of the adsorbent, and an HETP value of 0.16 mm was obtained for a particle diameter of 60 mum. Numerical simulation results suggested that the HETP value can be possibly reduced to the order of 10 mum by using an adsorbent with a particle diameter of 5 mum.

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Chiral Catalysts,
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