Mécanismes de transfert de proton d’une réaction acido-basique en phase aqueuse : une étude ab-initio

Les réactions de transfert de proton se retrouvent abondamment dans la nature et sont des processus cruciaux dans plusieurs réactions chimiques et biologiques, qui se produisent souvent en milieu aqueux. Les mécanismes régissant ces échanges de protons sont complexes et encore mal compris, suscitant un intérêt des chercheurs en vue d’une meilleure compréhension fondamentale du processus de transfert. Le présent manuscrit présente une étude mécanistique portant sur une réaction de transfert de proton entre un acide (phénol fonctionnalisé) et une base (ion carboxylate) en phase aqueuse. Les résultats obtenus sont basés sur un grand nombre de simulations de dynamique moléculaire ab-initio réalisées pour des systèmes de type « donneur-pont-accepteur », où le pont se trouve à être une unique molécule d’eau, permettant ainsi l’élaboration d’un modèle cinétique détaillé pour le système étudié. La voie de transfert principalement observée est un processus ultra-rapide (moins d’une picoseconde) passant par la formation d’une structure de type « Eigen » (H9O4+) pour la molécule d’eau pontante, menant directement à la formation des produits. Une seconde structure de la molécule d’eau pontante est également observée, soit une configuration de type « Zündel » (H5O2+) impliquant l’accepteur de proton (l’ion carboxylate) qui semble agir comme un cul-de-sac pour la réaction de transfert de proton.

Molecular mixed-valence cyanide bridged Co-III-Fe-II complexes

Cyano-bridged mixed-valence compounds have been known for a long time, i.e., Prussian Blue polymeric solids. Nevertheless, the interest in discrete complexes having a well-defined molecular nuclearity has emerged more recently. There are numerous examples of cyano-bridged mixed-valence complexes in the recent literature, as they show promising and useful applications in electrochromism, molecular magnetism and molecular electronics. In this paper, the reactivity, synthetic and structural chemistry, as well as some physical and chemical properties, of a series of discrete dinuclear mixed-valence cyano-bridged complexes of general formulae [LnCoIII(mu NC)Fe-II(CN)(5)](-) (L = pentadentate macrocyclic ligand) are reviewed. Special emphasis is given to the synthetic strategy, redox properties and metal-to-metal-charge-transfer (MMCT) band energy. Tuning the MMCT transition energy has been possible by changing the redox potential of the metal centers, both through structural and outer-sphere changes. The redox processes that involve the appearance and disappearance of these MMCT bands in the visible region have been dealt with in relation to the possible uses of the complexes. (c) 2004 Elsevier B.V. All rights reserved.

Methacryloxyethyl phosphate-grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2-butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGyh(-1)), monomer concentration (1-40 %) and solvent were studied and the modified membranes were characterized by weight increase, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C-F (ePTFE membrane) and the C-C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non-solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. (c) 2005 Society of Chemical Industry.

Direct electrochemistry of human and rat NADPH cytochrome P450 reductase

The diflavo-protein NADPH cytochrome P450 reductase (CPR) is the key electron transfer partner for all drug metabolizing cytochrome P450 enzymes in humans. The protein delivers, consecutively, two electrons to the heme active site of the P450 in a carefully orchestrated process which ultimately leads to the generation of a high valent oxo-heme moiety. Despite its central role in P450 function, no direct electrochemical investigation of the purified protein has been reported. Here we report the first voltammetric study of purified human CPR where responses from both the FMN and FAD cofactors have been identified using both cyclic and square wave voltammetry. For human CPR redox responses at -2 and -278 mV (with a ratio of 1e(-):3e(-)) vs NHE were seen at pH 7.9 while the potentials for rat CPR at pH 8.0 were -20 and -254 mV. All redox responses exhibit a pH dependence of approximately -59 mV/pH unit consistent with proton coupled electron transfer reactions of equal stoichiometry. (c) 2006 Elsevier B.V. All rights reserved.

Computationsl modelling of dimethyl ether separation and steam reforming in fluidized bed reactors

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether (DME) gas adsorptive separation and steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). Hydrogen is currently receiving increasing interest as an alternative source of clean energy and has high potential applications, including the transportation sector and power generation. Computational fluid dynamic (CFD) modelling has attracted considerable recognition in the engineering sector consequently leading to using it as a tool for process design and optimisation in many industrial processes. In most cases, these processes are difficult or expensive to conduct in lab scale experiments. The CFD provides a cost effective methodology to gain detailed information up to the microscopic level. The main objectives in this project are to: (i) develop a predictive model using ANSYS FLUENT (CFD) commercial code to simulate the flow hydrodynamics, mass transfer, reactions and heat transfer in a large scale dual fluidized bed system for combined gas separation and steam reforming processes (ii) implement a suitable adsorption models in the CFD code, through a user defined function, to predict selective separation of a gas from a mixture (iii) develop a model for dimethyl ether steam reforming (DME-SR) to predict hydrogen production (iv) carry out detailed parametric analysis in order to establish ideal operating conditions for future industrial application. The project has originated from a real industrial case problem in collaboration with the industrial partner Dow Corning (UK) and jointly funded by the Engineering and Physical Research Council (UK) and Dow Corning. The research examined gas separation by adsorption in a bubbling bed, as part of a dual fluidized bed system. The adsorption process was simulated based on the kinetics derived from the experimental data produced as part of a separate PhD project completed under the same fund. The kinetic model was incorporated in FLUENT CFD tool as a pseudo-first order rate equation; some of the parameters for the pseudo-first order kinetics were obtained using MATLAB. The modelling of the DME adsorption in the designed bubbling bed was performed for the first time in this project and highlights the novelty in the investigations. The simulation results were analysed to provide understanding of the flow hydrodynamic, reactor design and optimum operating condition for efficient separation. Bubbling bed validation by estimation of bed expansion and the solid and gas distribution from simulation agreed well with trends seen in the literatures. Parametric analysis on the adsorption process demonstrated that increasing fluidizing velocity reduced adsorption of DME. This is as a result of reduction in the gas residence time which appears to have much effect compared to the solid residence time. The removal efficiency of DME from the bed was found to be more than 88%. Simulation of the DME-SR in FLUENT CFD was conducted using selected kinetics from literature and implemented in the model using an in-house developed user defined function. The validation of the kinetics was achieved by simulating a case to replicate an experimental study of a laboratory scale bubbling bed by Vicente et al [1]. Good agreement was achieved for the validation of the models, which was then applied in the DME-SR in the large scale riser section of the dual fluidized bed system. This is the first study to use the selected DME-SR kinetics in a circulating fluidized bed (CFB) system and for the geometry size proposed for the project. As a result, the simulation produced the first detailed data on the spatial variation and final gas product in such an industrial scale fluidized bed system. The simulation results provided insight in the flow hydrodynamic, reactor design and optimum operating condition. The solid and gas distribution in the CFB was observed to show good agreement with literatures. The parametric analysis showed that the increase in temperature and steam to DME molar ratio increased the production of hydrogen due to the increased DME conversions, whereas the increase in the space velocity has been found to have an adverse effect. Increasing temperature between 200 oC to 350 oC increased DME conversion from 47% to 99% while hydrogen yield increased substantially from 11% to 100%. The CO2 selectivity decreased from 100% to 91% due to the water gas shift reaction favouring CO at higher temperatures. The higher conversions observed as the temperature increased was reflected on the quantity of unreacted DME and methanol concentrations in the product gas, where both decreased to very low values of 0.27 mol% and 0.46 mol% respectively at 350 °C. Increasing the steam to DME molar ratio from 4 to 7.68 increased the DME conversion from 69% to 87%, while the hydrogen yield increased from 40% to 59%. The CO2 selectivity decreased from 100% to 97%. The decrease in the space velocity from 37104 ml/g/h to 15394 ml/g/h increased the DME conversion from 87% to 100% while increasing the hydrogen yield from 59% to 87%. The parametric analysis suggests an operating condition for maximum hydrogen yield is in the region of 300 oC temperatures and Steam/DME molar ratio of 5. The analysis of the industrial sponsor’s case for the given flow and composition of the gas to be treated suggests that 88% of DME can be adsorbed from the bubbling and consequently producing 224.4t/y of hydrogen in the riser section of the dual fluidized bed system. The process also produces 1458.4t/y of CO2 and 127.9t/y of CO as part of the product gas. The developed models and parametric analysis carried out in this study provided essential guideline for future design of DME-SR at industrial level and in particular this work has been of tremendous importance for the industrial collaborator in order to draw conclusions and plan for future potential implementation of the process at an industrial scale.

Pseudoperiodic "Living" and/or controlled cationic ring-opening copolymerization of oxetane with tetrahydropyran:microstructure of polymers vs kinetics of chain growth

The "living" and/or controlled cationic ring-opening bulk copolymerization of oxetane (Ox) with tetrahydropyran (THP) (cyclic ether with no homopolymerizability) at 35°C was examined using ethoxymethyl-1 -oxoniacyclohexane hexafluoroantimonate (EMOA) and (BF3 · CH3OH)THP as fast and slow initiator, respectively, yielding living and nonliving polymers with pseudoperiodic sequences (i.e., each pentamethylene oxide fragment inserted into the polymer is flanked by two trimethylene oxide fragments). Good control over number-average molecular weight (Mn up to 150000 g mol-1) with molecular weight distribution (MWD ∼ 1.4-1, 5) broader than predicted by the Poison distribution (MWDs > 1 +1/DPn) was attained using EMOA as initiating system, i.e., C 2H5OCH2Cl with 1.1 equiv of AgSbF6 as a stable catalyst and 1.1 equiv of 2,6-di-tert-butylpyridine used as a non-nucleophilic proton trap. With (BF3 · CH 3OH)THP, a drift of the linear dependence M n(GPC) vs Mn(theory) to lower molecular weight was observed together with the production of cyclic oligomers, ∼3-5% of the Ox consumed in THP against ∼30% in dichloromethane. Structural and kinetics studies highlighted a mechanism of chains growth where the rate of mutual conversion between "strain ACE species" (chain terminated by a tertiary 1-oxoniacyclobutane ion, Al) and "strain-free ACE species" (chain terminated by a tertiary 1-oxoniacyclohexane ion, Tl) depends on the rate at which Ox converts the stable species T1 (kind of "dormant" species) into a living "propagating" center A1 (i.e., k aapp[Ox]). The role of the THP solvent associated with the suspension of irreversible and reversible transfer reactions to polymer, when the polymerization is initiated with EMOA, was predicted by our kinetic considerations. The activation -deactivation pseudoequilibrium coefficient (Qt) was then calculated in a pure theoretical basis. From the measured apparent rate constant of Ox (kOxapp) and THP (kTHPapp = ka(endo)app) consumption, Qt and reactivity ratio (kp/kd, k a(endo)/ka(exo), and ks/ka(endo) were calculated, which then allow the determination of the transition rate constant of elementary step reactions that governs the increase of Mu with conversion. © 2009 American Chemical Society.

Coherent rho meson electroproduction off deuteron

QCD predicts Color Transparency (CT), which refers to nuclear medium becoming transparent to a small color neutral object produced in high momentum transfer reactions, due to reduced strong interaction. Despite several studies at BNL, SLAC, FNAL, DESY and Jefferson Lab, a definitive signal for CT still remains elusive. In this dissertation, we present the results of a new study at Jefferson Lab motivated by theoretical calculations that suggest fully exclusive measurement of coherent rho meson electroproduction off the deuteron is a favorable channel for studying CT. Vector meson production has a large cross section at high energies, and the deuteron is the best understood and simplest nuclear system. Exclusivity allows the production and propagation to be controlled separately by controlling Q 2, lf (formation length), lc (coherence length) and t. This control is important as the rapid expansion of small objects increases their interaction probability and masks CT. The CT signal is investigated in a ratio of cross sections at high t (where re-scattering is significant) to low t (where single nucleon reactions dominate). The results are presented over a Q2 range of 1 to 3 GeV2 based on the data taken with beam energy of 6 GeV.

High energy three -body breakup of three -nucleon systems

The main goal of this dissertation was to study two- and three-nucleon Short Range Correlations (SRCs) in high energy three-body breakup of 3He nucleus in 3He(e, e'NN) N reaction. SRCs are characterized by quantum fluctuations in nuclei during which constituent nucleons partially overlap with each other. ^ A theoretical framework is developed within the Generalized Eikonal Approximation (GEA) which upgrades existing medium-energy methods that are inapplicable for high momentum and energy transfer reactions. High momentum and energy transfer is required to provide sufficient resolution for probing SRCs. GEA is a covariant theory which is formulated through the effective Feynman diagrammatic rules. It allows self-consistent calculation of single and double re-scatterings amplitudes which are present in three-body breakup processes. The calculations were carried out in detail and the analytical result for the differential cross section of 3He(e, e'NN)N reaction was derived in a form applicable for programming and numerical calculations. The corresponding computer code has been developed and the results of computation were compared to the published experimental data, showing satisfactory agreement for a wide range of values of missing momenta. ^ In addition to the high energy approximation this study exploited the exclusive nature of the process under investigation to gain more information about the SRCs. The description of the exclusive 3He( e, e'NN)N reaction has been done using the formalism of the nuclear decay function, which is a practically unexplored quantity and is related to the conventional spectral function through the integration of the phase space of the recoil nucleons. Detailed investigation showed that the decay function clearly exhibits the main features of two- and three-nucleon correlations. Four highly practical types of SRCs in 3He nucleus were discussed in great detail for different orders of the final state re-interactions using the decay function as an unique identifying tool. ^ The overall conclusion in this dissertation suggests that the investigation of the decay function opens up a completely new venue in studies of short range nuclear properties. ^

High energy three-body breakup of three-nucleon systems

The main goal of this dissertation was to study two- and three-nucleon Short Range Correlations (SRCs) in high energy three-body breakup of 3He nucleus in 3He(e, e'NN)N reaction. SRCs are characterized by quantum fluctuations in nuclei during which constituent nucleons partially overlap with each other. A theoretical framework is developed within the Generalized Eikonal Approximation (GEA) which upgrades existing medium-energy methods that are inapplicable for high momentum and energy transfer reactions. High momentum and energy transfer is required to provide sufficient resolution for probing SRCs. GEA is a covariant theory which is formulated through the effective Feynman diagrammatic rules. It allows self-consistent calculation of single and double re-scatterings amplitudes which are present in three-body breakup processes. The calculations were carried out in detail and the analytical result for the differential cross section of 3He(e, e'NN)Nreaction was derived in a form applicable for programming and numerical calculations. The corresponding computer code has been developed and the results of computation were compared to the published experimental data, showing satisfactory agreement for a wide range of values of missing momenta. In addition to the high energy approximation this study exploited the exclusive nature of the process under investigation to gain more information about the SRCs. The description of the exclusive 3He(e, e'NN)N reaction has been done using the formalism of the nuclear decay function, which is a practically unexplored quantity and is related to the conventional spectral function through the integration of the phase space of the recoil nucleons. Detailed investigation showed that the decay function clearly exhibits the main features of two- and three-nucleon correlations. Four highly practical types of SRCs in 3He nucleus were discussed in great detail for different orders of the final state re-interactions using the decay function as an unique identifying tool. The overall conclusion in this dissertation suggests that the investigation of the decay function opens up a completely new venue in studies of short range nuclear properties.

Experimental and Theoretical Models to Probe Mechanisms of Biological Charge Flow

Nature is challenged to move charge efficiently over many length scales. From sub-nm to μm distances, electron-transfer proteins orchestrate energy conversion, storage, and release both inside and outside the cell. Uncovering the detailed mechanisms of biological electron-transfer reactions, which are often coupled to bond-breaking and bond-making events, is essential to designing durable, artificial energy conversion systems that mimic the specificity and efficiency of their natural counterparts. Here, we use theoretical modeling of long-distance charge hopping (Chapter 3), synthetic donor-bridge-acceptor molecules (Chapters 4, 5, and 6), and de novo protein design (Chapters 5 and 6) to investigate general principles that govern light-driven and electrochemically driven electron-transfer reactions in biology. We show that fast, μm-distance charge hopping along bacterial nanowires requires closely packed charge carriers with low reorganization energies (Chapter 3); singlet excited-state electronic polarization of supermolecular electron donors can attenuate intersystem crossing yields to lower-energy, oppositely polarized, donor triplet states (Chapter 4); the effective static dielectric constant of a small (~100 residue) de novo designed 4-helical protein bundle can change upon phototriggering an electron transfer event in the protein interior, providing a means to slow the charge-recombination reaction (Chapter 5); and a tightly-packed de novo designed 4-helix protein bundle can drastically alter charge-transfer driving forces of photo-induced amino acid radical formation in the bundle interior, effectively turning off a light-driven oxidation reaction that occurs in organic solvent (Chapter 6). This work leverages unique insights gleaned from proteins designed from scratch that bind synthetic donor-bridge-acceptor molecules that can also be studied in organic solvents, opening new avenues of exploration into the factors critical for protein control of charge flow in biology.

Efectos de la microestructura sobre la transmisión de neutrones en materiales de interés nuclear.

Cuando un haz policromático de neutrones pasa a través de un material, los neutrones de distintas longitudes de onda son atenuados en formas muy diferentes. Como resultado, el espectro de energía del haz de neutrones cambia cuando una muestra es colocada frente el haz. Un análisis detallado del cociente de intensidad entre los haces de transmitido e incidente puede proporcionar una gran cantidad de información acerca de la estructura cristalina y microestructura de la muestra, definidas a través de la sección eficaz total del material. Para neutrones térmicos y sub-térmicos, el ordenamiento y movimiento de los átomos a escala microscópica define en forma precisa la dependencia de esta magnitud con la energía del neutrón incidente. Así, la variación con la energía de la sección eficaz total de los sólidos debido a la estructura de los átomos para distancias entre 0,1 y 100 Å se encuentra bien establecida, y es explotada en el estudio de estructuras cristalinas y de los movimientos vibracionales y rotacionales. Como contrapartida, el efecto de la estructura mesoscópica de los materiales, esto es para dimensiones entre 0,1 y 100 µm, sobre la sección eficaz total ha sido mucho menos estudiado, a pesar de provocar cambios profundos en esta magnitud. En esta Tesis estudiamos y formalizamos la dependencia de la sección eficaz total con características microestructurales tales como la porosidad, y la distribución de tamaños y orientaciones de los granos que componen los materiales, y desarrollamos modelos teóricos a partir de las características microestructurales de muestras de interés nuclear con diferente microestructura. Estos modelos permiten describir la contribuci ón de la componente elástica coherente de la seción eficaz total sobre los espectros de transmisión de neutrones e introducen parámetros como la cantidad de cristales que conforman el material, su estructura cristalina, parámetros de red, mosaicidad, estructura de poros u orientación preferencial de granos, para describir la sección total de materiales monocristalinos o policristalinos. En todos los casos, los modelos desarrollados fueron implementados en una biblioteca basada en el lenguaje computacional MATLAB y fueron comparados con secciones eficaces totales obtenidas en experimentos de transmisión de neutrones realizados en el Departamento de Física de Neutrones del Centro Atómico Bariloche y en ISIS Facility, Reino Unido. Los novedosos modelos microestructurales propuestos describen fielmente los experimentos desarrollados sobre muestras con distinta microestructura, lo que permite el empleo de los mismos en un código de refinamiento sobre los datos experimentales. Aquí, desarrollamos herramientas computacionales que ajustan por cuadrados mínimos no lineales los modelos paramétricos representativos de cada microestructura, sobre la sección eficaz total o la transmisión experimental, para determinar parámetros microestructurales de la muestra a partir de experimentos de transmisión de neutrones con resolución en longitud de onda. Los resultados son de particular relevancia para la interpretación y el análisis cuantitativo de las imágenes realizadas por la técnica de radiografía neutrónica con resolución en energía, que ha recibido un gran impulso en años recientes.

Efectos de la microestructura sobre la transmisión de neutrones en materiales de interés nuclear.

Cuando un haz policromático de neutrones pasa a través de un material, los neutrones de distintas longitudes de onda son atenuados en formas muy diferentes. Como resultado, el espectro de energía del haz de neutrones cambia cuando una muestra es colocada frente el haz. Un análisis detallado del cociente de intensidad entre los haces de transmitido e incidente puede proporcionar una gran cantidad de información acerca de la estructura cristalina y microestructura de la muestra, definidas a través de la sección eficaz total del material. Para neutrones térmicos y sub-térmicos, el ordenamiento y movimiento de los átomos a escala microscópica define en forma precisa la dependencia de esta magnitud con la energía del neutrón incidente. Así, la variación con la energía de la sección eficaz total de los sólidos debido a la estructura de los átomos para distancias entre 0,1 y 100 Å se encuentra bien establecida, y es explotada en el estudio de estructuras cristalinas y de los movimientos vibracionales y rotacionales. Como contrapartida, el efecto de la estructura mesoscópica de los materiales, esto es para dimensiones entre 0,1 y 100 µm, sobre la sección eficaz total ha sido mucho menos estudiado, a pesar de provocar cambios profundos en esta magnitud. En esta Tesis estudiamos y formalizamos la dependencia de la sección eficaz total con características microestructurales tales como la porosidad, y la distribución de tamaños y orientaciones de los granos que componen los materiales, y desarrollamos modelos teóricos a partir de las características microestructurales de muestras de interés nuclear con diferente microestructura. Estos modelos permiten describir la contribuci ón de la componente elástica coherente de la seción eficaz total sobre los espectros de transmisión de neutrones e introducen parámetros como la cantidad de cristales que conforman el material, su estructura cristalina, parámetros de red, mosaicidad, estructura de poros u orientación preferencial de granos, para describir la sección total de materiales monocristalinos o policristalinos. En todos los casos, los modelos desarrollados fueron implementados en una biblioteca basada en el lenguaje computacional MATLAB y fueron comparados con secciones eficaces totales obtenidas en experimentos de transmisión de neutrones realizados en el Departamento de Física de Neutrones del Centro Atómico Bariloche y en ISIS Facility, Reino Unido. Los novedosos modelos microestructurales propuestos describen fielmente los experimentos desarrollados sobre muestras con distinta microestructura, lo que permite el empleo de los mismos en un código de refinamiento sobre los datos experimentales. Aquí, desarrollamos herramientas computacionales que ajustan por cuadrados mínimos no lineales los modelos paramétricos representativos de cada microestructura, sobre la sección eficaz total o la transmisión experimental, para determinar parámetros microestructurales de la muestra a partir de experimentos de transmisión de neutrones con resolución en longitud de onda. Los resultados son de particular relevancia para la interpretación y el análisis cuantitativo de las imágenes realizadas por la técnica de radiografía neutrónica con resolución en energía, que ha recibido un gran impulso en años recientes.

Organometallic chemistry of diphosphazanes. Part 26. Ruthenium hydride complexes of chiral and achiral diphosphazane ligands and asymmetric transfer hydrogenation reactions

The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(eta(5)-Cp)RuCl{kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] [R = C6H3Me2-2,6] (1) and [(eta(5)-Cp*)RuCl{kappa(2)-P, P-X2PN(R)PYY'}] [R = Me, X = Y = Y' = OC6H5 (2); R = CHMe2, X-2 = C20H12O2, Y = Y' = OC6H5 (3) or OC6H4'Bu-4 (4)] have been prepared by the reaction of CpRu(PPh3)(2)Cl with (RO)(2)PN(Me)P(OR)(2) [R = C6H3Me2-2,6 (L-1)] or by the reaction of [Cp*RuCl2](n) with X2PN(R)PYY' in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the "chiral at metal" complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(eta(5)-Cp)RuCl {kappa(2)-P,P-Ph2PN((S)-*CHMePh)PPhY)] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(eta(5) -Cp)RuH {kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] (7), [(eta(5)-Cp*)RuH {kappa(2)-P,P'-X2PN(R)PY2)] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X-2 = C20H12O2, Y = OC6H4'Bu-4 (9)] and [(eta(5) -Cp)RuH(kappa(2)-P, P-Ph2PN((S)-*CHMePh)PPhY)][Y =Ph (10) or N2C3HMe2-3,5 (SCSPRRu)(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(eta(5)- Cp)Ru(eta(2)-H-2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2))]X (12a) and [(eta(5)-Cp)Ru(H)(2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2)}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T, measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong pi-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){kappa(2)-P,P-X2PN(R)PY2)(solvent)(2)] could be the active species in this transformation. (c) 2007 Elsevier B.V. All rights reserved.

Padé approach to potential transients: Part 1. Electron transfer without and with coupling to first-order homogeneous reactions at planar electrodes

Potential transients are obtained by using “Padé approximants” (an accurate approximation procedure valid globally — not just perturbatively) for all amplitudes of concentration polarization and current densities. This is done for several mechanistic schemes under constant current conditions. We invert the non-linear current-potential relationship in the form (using the Lagrange or the Ramanujan method) of power series appropriate to the two extremes, namely near reversible and near irreversible. Transforming both into the Pad́e expressions, we construct the potential-time profile by retaining whichever is the more accurate of the two. The effectiveness of this method is demonstrated through illustrations which include couplings of homogeneous chemical reactions to the electron-transfer step.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.