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A series of Group 2 metal bis(arenecarbochalcogenoato)(crown ether) complexes M(EE?CAr)2(L)(L?)x (M = Mg, Ca, Sr, Ba; Ar = aryl; E = S, Se; E? = O, S; L = H2O or THF; L? = 15-crown-5, 18-crown-6) were synthesized and their structures were revealed by X-ray analyses. The two carbothioato ligands in Mg, Ca and Sr 15-crown-5 complexes are located on the same side of the crown ether plane, while those in Mg, Ca, Sr, and Ba 18-crown-6 compounds are on both sides of the 18-crown-6 plane (trans relative to the plane). For the Ca 15-crown-5 complex, both carbothioato ligands are connected to the central Ca ion through an oxygen atom in a monodentate manner, and the two hydrogen atoms of the coordinated water molecule are intramolecularly hydrogen-bonded with thiocarbonyl sulfur atoms. One of the two carbothioate groups in the Ca 18-crown-6 complex is connected in a bidentate manner to the central metal, while the other is connected in a monodentate manner through an oxygen atom. The two thiocarboxylato ligands in the Sr 15-crown-5 congener are connected in a bidentate fashion to the same side of the crown ether plane. The Ca and Sr compounds are the first examples of alkali earth metal carbochalcogenoate complexes in which carbochalcogenolato ligands are connected in a monodentate manner through an oxygen atom. Both chalcogenoato ligands in Ba(SOCC6H4Me-4)2(18-crown-6) and Sr(SeOCC6H4Me-4)2(18-crown-6) are coordinated in a bidentate manner to the central metal ion.

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Methyl benzoate, N,N-dimethylbenzamide, and benzophenone were reduced by UIII[N(SiMe3)2]3 resulting in uranium(IV) products. Reduction of benzophenone lead to UIV[OC?Ph2)][N(SiMe3)2]3, (1.1) which forms the dinuclear complex, [N(SiMe3)2]3UIV(OCPhPh-CPh2O)UIV[N(SiMe3)2]3 (1.2), through coupling of the ketyl radical species upon crystallization. Reaction of N,N-dimethylbenzamide with UIII[N(SiMe3)2]3 resulted in UIV[OC?(Ph)(NMe2)][N(SiMe3)2]3 (2), a uranium(IV) compound and the first example of a charge-separated amide radical. In the case of methyl benzoate, the reduction resulted in UIV(OMe)[N(SiMe3)2]3 (3) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded UV(=NSiMe3)[N(SiMe3)2]3. Additionally, 2 was reduced with potassium graphite resulting in [U(mu-O)[O=C(NMe2)(Ph)][N(SiMe3)2]2]2 (4), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15-crown-5 afforded isolation of the mono-oxo compound, [(15-crown-5)2K][UO[N(SiMe3)2]3] (5). The results expand the reduction capabilities of UIII complexes and demonstrate a strategy for isolating novel metal-stabilized radicals.

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The process of potassium metal dissolution in tetrahydrofuran containing 15-crown-5 and the properties of the solution were studied.The changes in concentration of potassium anions and electrons as a function of time were determined by means of (39)K NMR and ESR spectroscopies.Enhanced stability of the solution with 15-crown-5 relative to that containing 18-crown-6 or 12-crown-4 was revealed.

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Chiral Catalysts,
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Paramagnetic complexes of the type [N3N]MoL ([N3N]3- = [(Me3SiNCH2CH2)3N]3-; L = CO, RNC, C2H4) have been prepared by displacing dinitrogen from [N3N]Mo(N2). [N3N]Mo-(CO) was reduced by magnesium powder in the presence of Me3SiCl to yield the diamagnetic oxycarbyne complex [N3N]Mo?COSiMe3, while oxidation of [N3N]Mo(CN-t-Bu) with [Cp2-Fe]OTf yielded {[N3N]Mo(CN-t-Bu)}OTf. Thermolysis of [N3N]Mo(CN-t-Bu) resulted in loss of a t-Bu radical to yield [N3N]Mo(CN), which was structurally characterized. [N3NF]ML ([N3NF]3- = [(C6F5NCH2CH2)3N] 3-; M = Mo, W; L = CO, RNC) complexes have been prepared by one-electron reduction of [N3NF]M(OTf) in the presence of L. An X-ray study of [N3NF]W-(CN-t-Bu) showed it to contain a bent isocyanide ligand. Anionic CO complexes were prepared by the two-electron reduction of [N3NF]M(OTf) in the presence of CO. An X-ray study of {[N3NF]W(CO)2}Na(ether)3 revealed it to have a pseudo-octahedral structure in which sodium is bound to the CO trans to the amine donor atom. Treatment of {[N3NF]M(CO)}- complexes with Me3SiCl gave oxycarbyne complexes [N3NF]M?COSiMe3. Reaction of [N3NF]WCO with V(Mes)3(THF) yielded [N3NF]W(CO)V(Mes)3, the structure of which was determined in an X-ray study. Cationic [N3Np]3- complexes could be prepared that contain up to 3 equiv of isocyanide. An X-ray study of {[N3NF]W(CN-t-Bu)3}BPh4 showed it to be a seven-coordinate species with one isocyanide located in the equatorial plane and the other two isocyanide ligands in the apical pocket. Reduction of [N3NF]W(OTf) under ethylene gave [N3NF]W(C2H4), which could be oxidized to yield diamagnetic {[N3NF]W(C2H4)}OTf.

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Chiral Catalysts,
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The direct alkenylation of C(sp3)-H bonds was achieved by employing benzophenone and 1,2-bis(phenylsulfonyl)ethylene under photo-irradiation conditions. This simple metal-free reaction enables the substitution of heteroatom-substituted methine, methylene and aliphatic C(sp3)-H bonds by (E)-sulfonylalkene units in a highly chemoselective manner. The derived sulfonylalkenes were further converted in a single step to the prenyl derivatives via a second photo-induced radical substitution and to the pyrrole derivatives via cyclization and aromatization steps. The present protocol thus serves as an efficient method for the direct extension of carbon skeletons for the synthesis of structurally complex natural products and pharmaceuticals. This journal is

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Chiral Catalysts,
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The equilibrium constant of extraction of lithium, sodium, or potassium picrates, MPi, with 18-crown-6 or dibenzo-18-crown-6 between water and dichloromethane was determined spectrophotometrically and compared with literature values. In all instances, a 1:1:1 complex was extracted. The value of the ionic association constant of the complexed potassium picrate in the organic phase agrees well with that from electrolytic conductivity data. The latter reveals the presence of both cationic and anionic ion triplets in solutions >3 × 10-3 mol-1 dm-3. The effect of temperature on the solubility of dibenzo-18-crown-6 in water saturated with dichloromethane yields DeltaH = -16.4 kJ mol-1 and DeltaS = -36.02 kJ mol-1 K-1. Values of the activity coefficient of dibenzo-18-crown-6 at 296.1 K (“salting out effect”) in aqueous lithium chloride (0.10 to 0.25 mol dm-3) were estimated from the effect of the salt on the solubility, while the activity coefficient of the crown ether in dichlaromethane saturated with water was evaluated from the effect of the salt on the partition coefficient. An estimate of the activity coefficient product, y(K+)y(Pi-), in the aqueous lithium chloride solutions was made from the effect of this electrolyte on the extraction constant.

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Chiral Catalysts,
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Page 2076. Erroneous values of speed of sound in water c1/ m.s-1 are reported in table. Correct values taken from reference 7 (Harvey, A. H.; Peskin, A. P.; Klein, S. A. NIST/ ASME Steam Properties, Formulation for General and Scientific Use. NIST Standard Reference Database 10, version 2.11, 1996) are in Table 2 below. Correct values were used for calculations of partial molar volumes and partial molar isentropic compressions.(table presented).

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The hydrodynamic equation D/T = alphaetabeta, where D is the infinite dilution binary diffusion or self-diffusion coefficient, T is the temperature, eta is the fluid viscosity, and alpha and beta are constants, were demonstrated to be effective for predicting both binary diffusion and self-diffusion coefficients in high density fluids, i.e. liquid and supercritical states. When a solute was specified, the correlation well represented both binary diffusion and self-diffusion coefficients, irrespective of solvent over a wide solvent viscosity range. The solute-dependent constants alpha and beta were determined for 12 solutes with average absolute deviation of 6.2% for 1006 data points.

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Chiral Catalysts,
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Complexation constants of the proton, Kf(LHS+), and of the hydronium ion, Kf(LH3O+), with a host of crown ethers (L) in acetonitrile have been determined.With 12-crown-4 the proton yielded LHS+ and (a sandwich complex?) L2HS+.The dibenzo effect in 18-crown-6-on Kf(LHS+) and Kf(L3O+) is 2 orders of magnitude greater than that on Kf(LK+).It is concluded that the proton as well as the hydronium ion is complexed by hydrogen bonding to the ether oxygens in addition to ion-dipole interaction with the oxygens.The exchange constant between LHS+ and Ag(1+) has been determined in propylene carbonate and found equal to the ratio of formation constants of the complexes.The mobility (lambda0) of the hydronium ion complex with dicyclohexano-18-crown-6 in acetonitrile (cis, syn, cis) has been found equal to 68.3 (25 deg C) and is considerably greater than the literature value of 53.3 of the complex with potassium.

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In this study, the effect of reaction temperature, solvent and catalyst were examined on conversion of Trametes versicolor mushroom. Supercritical liquefaction experiments were made in a cylindrical reactor in acetone and isopropanol under supercritical circumstances with (Aluminium oxide, calcium hydroxide) and without catalyst at the temperatures of 250, 270, 290 C. The bio-oils obtained at 250 and 290 C in liquefaction were analyzed and characterized by chromatographic and spectroscopic techniques containing GC?MS, FT-IR and elemental analysis.

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Chiral Catalysts,
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