260 research outputs found

    Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex

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    A cobalt bis(iminopyridine) complex is a highly active electrocatalyst for water reduction, with an estimated apparent second order rate constant k_(app) ≤ 10^7 M^(–1)s^(–1) over a range of buffer/salt concentrations. Scan rate dependence data are consistent with freely diffusing electroactive species over pH 4–9 at room temperature for each of two catalytic reduction events, one of which is believed to be ligand based. Faradaic H_2 yields up to 87 ± 10% measured in constant potential electrolyses (−1.4 V vs SCE) confirm high reactivity and high fidelity in a catalyst supported by the noninnocent bis(iminopyridine) ligand. A mechanism involving initial reduction of Co^(2+) and subsequent protonation is proposed

    Diseño y desarrollo de un sistema de facturación web para el restaurante Paseo Azteca

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    Tesis(Ingeniero en Sistema)--Universidad Americana, Managua, 2016La presente tesis nos presenta un sistema de facturación con el objetivo de llevar un control de los movimientos de las ventas y de los inventarios para lograr una mejor planificación de los recursos, reduciendo un margen de error humano y el tiempo de procesamiento permitiendo incrementar la productividad

    Wi2Fly

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    Seminario Desarrollo de Emprendedores. 2013. Carrera Ingeniería Industrial y Sistema .Micro empresa del sector tecnológico - publicitario que ofrece FLYNET, un servicio que permite mostrar anuncios publicitarios en la pantalla de dispositivos electrónicos mientras el usuario hace uso de un servicio de internet de alta velocidad, en hotspots ubicados estratégicamente en diversos puntos en la ciudad de Managua. Los hotsposts, o lugares de antena de WiFi, son centros comerciales, universidad y otras plazas públicas. Para poder brindar el servicio, WI2FLY necesita de dispositivos tecnológicos, como una antena WAVION y servicio de un ISP( Internet Service Provider) con un ancho de banda mayor a 10 Mbps empresariales. La empresa se ubica en residencial Los Robles

    Relative Reactivity of the Metal-Amido versus Metal-Imido Bond in Linked Cp-Amido and Half-Sandwich Complexes of Vanadium

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    Treatment of (η5-C5H4C2H4NR)V(N-t-Bu)Me (R = Me, i-Pr) and CpV(N-p-Tol)(N-i-Pr2)Me (Cp = η5-C5H5) with B(C6F5)3 or [Ph3C][B(C6F5)4] results in formation of the corresponding cations, [(η5-C5H4C2H4NR)V(N-t-Bu)]+ and [CpV(N-p-Tol)(N-i-Pr2)]+. The latter could also be generated as its N,N-dimethylaniline adduct by treatment of the methyl complex with [PhNMe2H][BAr4] (Ar = Ph, C6F5). Instead, the analogous reaction with the linked Cp-amido precursor results in protonation of the imido-nitrogen atom. Sequential cyclometalation of the amide substituents gave cationic imine complexes [(η5-C5H4C2H4NCR'2)V(NH-t-Bu)]+ (R' = H, Me) and methane. Reaction of cationic [(η5-C5H4C2H4NR)V(N-t-Bu)]+ with olefins affords the corresponding olefin adducts, whereas treatment with 1 or 2 equiv of 2-butyne results in insertion of the alkyne into the vanadium-nitrogen single bond, affording the mono- and bis-insertion products [(η5-C5H4C2H4N(i-Pr)C2Me2)V(N-t-Bu)]+ and [(η5-C5H4C2H4N(i-Pr)C4Me4)V(N-t-Bu)]+. The same reaction with the half-sandwich compound [CpV(N-p-Tol)(N-i-Pr2)]+ results in a paramagnetic compound that, upon alcoholysis, affords sec-butylidene-p-tolylamine, suggesting an initial [2+2] cycloaddition reaction. The difference in reactivity between the V-N bond versus the V=N bond was further studied using computational methods. Results were compared to the isoelectronic titanium system CpTi(NH)(NH2). These studies indicate that the kinetic product in each system is derived from a [2+2] cycloaddition reaction. For titanium, this was found as the thermodynamic product as well, whereas the insertion reaction was found to be thermodynamically more favorable in the case of vanadium.

    Neutral and Cationic Rare Earth Metal Alkyl and Benzyl Compounds with the 1,4,6-Trimethyl-6-pyrrolidin-1-yl-1,4-diazepane Ligand and Their Performance in the Catalytic Hydroamination/Cyclization of Aminoalkenes

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    A new neutral tridentate 1,4,6-trimethyl-6-pyrrolidin-1-yl-1,4-diazepane (L) was prepared. Reacting L with trialkyls M(CH2SiMe3)3(THF)2 (M = Sc, Y) and tribenzyls M(CH2Ph)3(THF)3 (M = Sc, La) yielded trialkyl complexes (L)M(CH2SiMe3)3 (M = Sc, 1; M = Y, 2) and tribenzyl complexes (L)M(CH2Ph)3 (M = Sc, 3; M = La, 4). Complexes 1 and 2 can be converted to their corresponding ionic compounds [(L)M(CH2SiMe3)2(THF)][B(C6H5)4] (M = Sc, Y) by reaction with [PhNMe2H][B(C6H5)4] in THF. Complexes 3 and 4 can be converted to cationic species [(L)M(CH2Ph)2]+ by reaction with [PhNMe2H][B(C6F5)4] in C6D5Br in the absence of THF. The neutral complexes 1-4 and their cationic derivatives were studied as catalysts for the hydroamination/cyclization of 2,2-diphenylpent-4-en-1-amine and N-methylpent-4-en-1-amine reference substrates and compared with ligand-free Sc, Y, and La neutral and cationic catalysts. The most effective catalysts in the series were the cationic L-yttrium catalyst (for 2,2-diphenylpent-4-en-1-amine) and the cationic lanthanum systems (for N-methylpent-4-en-1-amine). For the La catalysts, evidence was obtained for release of L from the metal during catalysis.

    Electrocatalytic hydrogen evolution by an iron complex containing a nitro-functionalized polypyridyl ligand

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    Iron polypyridyl complexes have recently been reported to electrocatalytically reduce protons to hydrogen gas at -1.57 V versus Fc(+)/Fc. A new iron catalyst with a nitro-functionalized polypyridyl ligand has been synthesized and found to be active for proton reduction. Interestingly, catalysis occurs at -1.18 V versus Fc(+)/Fc for the nitro-functionalized complex, resulting in an overpotential of 300 mV. Additionally, the complex is active with a turnover frequency of 550 s(-1). Catalysis is also observed in the presence of water with a 12% enhancement in activity. (C) 2015 Elsevier Ltd. All rights reserved

    Cobalt-based molecular electrocatalysis of nitrile reduction: evolving sustainability beyond hydrogen

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    Two new cobalt bis-iminopyridines, [Co(DDP)(H2O)2](NO3)2 (1, DDP = cis-[1,3-bis(2-pyridinylenamine)] cyclohexane) and [Co(cis-DDOP)(NO3)](NO3) (2, cis-DDOP = cis-3,5-bis[(2- Pyridinyleneamin]-trans-hydroxycyclohexane) electrocatalyse the 4-proton, 4-electron reduction of acetonitrile to ethylamine. For 1, this reduction occurs in preference to reduction of protons to H2. A coordinating hydroxyl proton relay in 2 reduces the yield of ethylamine and biases the catalytic system back towards H2
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