The Absolute Best Science Experiment for 1,4,7,10,13-Pentaoxacyclopentadecane

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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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Chiral Catalysts,
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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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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare

Some scientific research about 33100-27-5

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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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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare

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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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The reactivity of terminal uranium(V/VI) nitrides with CE2(E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2to give [U(TrenTIPS)(O)(NCO)][K(B15C5)2] (3), whereas the uranium(VI) nitride [U(TrenTIPS)(N)] (2) reacts with CO2to give isolable [U(TrenTIPS)(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(TrenTIPS)(O)] (5) with concomitant formation of N2and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS2to give [U(TrenTIPS)(kappa2-CS3)][K(B15C5)2] (6), 2, and [K(B15C5)2][NCS] (7), whereas 2 reacts with CS2to give [U(TrenTIPS)(NCS)] (8) and ?S?, with the latter trapped as Ph3PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS2as a reactivity surrogate for CO2.

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Chiral Catalysts,
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(X = Cl, Br) and have been prepared by reactions of X2V(N3S2) with sodium fluoride in acetonitrile suspensions in the presence of 15-crown-5 and benzo-15-crown-5, respectively.The 15-N-labeled complex was also prepared and characterized by 15N, 19F, and 51V NMR spectra, as well as by IR spectroscopy.Whereas the crystal structure of , owing to disorder of the crown ether molecule, could be refined only to an R-value of 0.16 (space group C2/m, Z = 4, a = 1995.4(11); b = 1016.2(6); c = 1047.2(8) pm; beta = 100.83(4) deg at -65 deg C), the crystal structure of the corresponding was determined without complications.Space group P21/c, Z = 4, 5565 observed independent reflexion.R = 0.036.Lattic dimensions at 20 deg C; a = 1198.9(6); b = 970.3(5); c = 1918.2(10) pm; beta = 93.74(3) deg.The compound forms ion pairs, in which the sodium atom is seven-coordinated by the oxygen atoms of the crown ether molecule, the fluorine atom and one chlorine atom of the trigonal-bipyramidal – unit.The vanadium atom is part of a planar VN3S2 ring; fluorine and two nitrogen atoms of the cyclothiazeno ring occupy the equatorial positions. – Keywords: Fluoro-Chloro-Cyclothiazeno Complexes of Vanadium, 15N NMR Spectra; 51V NMR Spectra, IR Spectra, Crystal Structure

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Chiral Catalysts,
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Benzo-15-crown-5 (B15C5) extracted alkali metal picrates (MA) into benzene by forming M(B15C5)A or M(B15C5)//2A complexes and moreover, in the presence of tributyl phosphate (B), B15C5 extracted rubidium and cesium picrates by forming M(B15C5)BA complexes. The extractability sequences of the M(B15C5)A, MM(B15C5)//2A, and M(B15C5)BA complexes are Na** plus greater than K** plus greater than Rb** plus greater than Li** plus greater than Cs** plus , K** plus greater than Rb** plus greater than Cs** plus , and Rb** plus greater than Cs** plus respectively. The extraction equilibrium constants for these complexes have been determined at 25 degree C, and the synergistic formation constants of the M(B15C5)//2A and M(B15C5)BA complexes in the benzene solution have been calculated. The synergistic effects for the alkali metal ions for the B15C5 system were compared with those for the 15C5 system.

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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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A polyelectrolyte multilayer (PEM) coating consisting of the polypeptide, poly(L-lysine) hydrobromide, poly(L-lysine) and the polymeric dipeptide surfactant, poly(sodium undecanoyl-L-leutcyl-alaninate), poly(L-SULA), is investigated as a new medium for the separation of chiral analytes in open-tubular capillary electrochromatography (OT-CEC). In this approach, a stable PEM is constructed in situ by alternative rinses of the cationic polymer poly(L-lysine) and the anionic polymer poly(L-SULA). In previous studies, the PEM coating has been constructed by use of the cationic polyelectrolyte poly (diallydimethylammonium chloride), PDADMAC. In this study, we investigate the use of a biopolymer as the cationic polyelectrolyte. The results reported here indicate an increase in selectivity and resolution when poly(L-lysine) is used as the cationic polymer in place of PDADMAC. To evaluate the chromatographic performance of the PEM coating as a chiral stationary phase, the separation of the beta-blockers, labetalol and sotalol, and the binaphthyl derivatives, 1,1?-bi-2-naphthyl-2,2?-dihydrogen phosphate, 1,1?-bi-2- naphthol, and 1,1-binaphthyl-2,2?-diamine, are investigated. In addition, the effect of varying the amino acid order of the polymeric dipeptide surfactant on resolution is investigated. The number of bilayers also significantly influences the separation efficiency and resolution of enantiomers. The run-to-run and capillary-to-capillary reproducibilities are evaluated by calculating the relative standard deviations (RSDs) of the electroosmotic flow. These RSD values were found to be less than 1%. The coating is also stable and allows more than 290 runs to be performed in the same capillary. In addition, coupling of this chiral OT-CEC column with mass spectrometry is investigated.

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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare