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Bond Breaking (bond + breaking)
Selected AbstractsChemInform Abstract: Palladium-Catalyzed Diacetoxylation of Methylenecyclopropanes via C(sp3),C(sp3) Bond BreakingCHEMINFORM, Issue 11 2010Min Jiang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Arylation of Hydrocarbyl Ligands Formed from n -Alkanes through C,H Bond Activation of Benzene Using a Triruthenium ClusterEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2009Makoto Moriya Abstract Triruthenium complex 2 containing a perpendicularly coordinated 1-pentyne ligand, which is one of the key intermediates of the reaction of triruthenium pentahydrido complex 1 with n -pentane, reacts with benzene to yield ,3 -benzyne,,3 -pentylidyne complex 5 by C,H bond activation. ,-H elimination form the ,3 -penytylidyne ligand occurred upon heating to yield ,3 -pentenylidene complex 6, which was followed by the formation of closo -ruthenacyclopentadiene complex 8 by the connection of the two hydrocarbyl moieties placed on each face of the triruthenium plane with partial metal,metal bond breaking. Treatment of 8 with pressurized hydrogen resulted in exclusive liberation of n -pentylbenzene, which is difficult to synthesize by conventional Friedel,Crafts alkylation. These sequential transformations correspond to the formation of linear alkylbenzene by the reaction of pentane with benzene on a trimetallic plane. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross-Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by ,2 -(Dimethyl fumarate)(iminophosphane)palladium(0) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2004Bruno Crociani Abstract The complexes [Pd(,2 -dmfu)(P,N)] {dmfu = dimethyl fumarate; P,N = 2-(PPh2)C6H4,1-CH=NR, R = C6H4OMe-4 (1a), CHMe2 (2a), C6H3Me2 -2,6 (3a), C6H3(CHMe2)2 -2,6 (4a)} undergo dynamic processes in solution which consist of a P,N ligand site exchange through initial rupture of the Pd,N bond at lower energy and an olefin dissociation-association at higher energy. According to equilibrium constant values for olefin replacement, the complex [Pd(,2 -fn)(P,N)] (fn = fumaronitrile, 1b) has a greater thermodynamic stability than its dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3 -4) to 1a and 2a lead to the products [PdI(Ar)(P,N)] (1c, 2c) and obey the rate law, kobs = k1A + k2A[ArI]. The k1A step involves oxidative addition to a reactive species [Pd(solvent)(P,N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(,2 -dmfu)(solvent)(,1 -P,N)] formed in a pre-equilibrium step from Pd,N bond breaking. The complexes 1c and 2c react with PhC,CSnBu3 in the presence of an activated olefin (ol = dmfu, fn) to yield the palladium(0) derivatives [Pd(,2 -ol)(P,N)] along with ISnBu3 and PhC,CAr. The kinetics of the transmetallation step, which is rate-determining for the overall reaction, obey the rate law: kobs = k2T[PhC,CSnBu3]. The k2T values are markedly enhanced in more polar solvents such as CH3CN and DMF. The solvent effect and the activation parameters suggest an associative SE2 mechanism with substantial charge separation in the transition state. The kinetic data of the above reactions in various solvents indicate that, for the cross-coupling of PhC,CSnBu3 with ArI catalysed by 1a or 2a, the rate-determining step is represented by the oxidative addition and that CH3CN is the solvent in which the highest rates are observed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Ab initio and DFT calculations of benzaldoxime elimination kinetics in the gas phaseINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2008Jose R. Mora Abstract The mechanism for the gas-phase molecular elimination kinetics of benzaldoxime was examined at MP2/6-31G, MP2/6-31G(d,p), B3LYP/6-31G, B3LYP/6-31G(d,p), MPW1PW91/6-31G, and MPW1PW91/6-31G(d,p) levels of theory. The products of elimination of this oxime are benzonitrile and water. Calculated thermodynamic and kinetic parameters estimated from B3LYP/6-31G was found to be in better agreement with the experimental values. Transition state structure is best described as a four-membered cyclic structure with good approximation to planarity. NBO charges analysis revealed a little greater polarization of the benzylic C,H,+ rather than N,OH,,. Bond indexes and synchronicity parameters are in agreement with a concerted semi-polar type of mechanism with benzylic CH bond breaking as determining step of the reaction. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] (R,S)-Azolides as Novel Substrates for Lipase-Catalyzed Hydrolytic Resolution in Organic SolventsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009Pei-Yun Wang Abstract Azolides, that is, N -acylazoles, as versatile acylation reagents are well characterized in the literature, in which the azole structure can not only act as a better leaving group but also make the carbonyl carbon more electrophilic and susceptible to nucleophilic attack. It is therefore desirable to combine this unique property and lipase resolution ability in the development of a new resolution process for preparing optically pure carboxylic acids. With the Candida antarctica lipase B (CALB) - catalyzed hydrolysis of (R,S)- N -profenylazoles in organic solvents as the model system, (R,S)- N -profenyl-1,2,4-triazoles instead of their corresponding ester analogues were exploited as the best substrates for preparing optically pure profens, i.e., 2-arylpropionic acids. The structure-reactivity correlations for the (R,S)-azolides in water-saturated methyl tert -butyl ether (MTBE) at 45,°C coupled with a thorough kinetic analysis were further employed for elucidating the rate-limiting formation of a tetrahedral adduct without CN bond breaking or with moderate CN bond breaking concerted with CO bond formation in the acylation step. The advantages of easy substrate preparation, high enzyme reactivity and enantioselectivity, and easy recovery of the product and remaining substrate by aqueous extraction demonstrate the potential of using (R,S)-azolides as novel substrates for the enzymatic resolution process. [source] Mechanism and dynamics of organic reactions: 1,2-H shift in methylchlorocarbene,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8 2002Elfi Kraka Abstract The unified reaction valley approach (URVA) was used to investigate the mechanism of the rearrangement of methylchlorocarbene to chloroethene [reaction(1)] in the gas phase with special emphasis on the role of H tunneling. The reaction valley of (1) was explored using different methods (HF, MP2 and DFT/B3LYP) and different basis sets [6,31G(d), 6,31G(d,p) and cc-pVTZ]. Results were analyzed characterizing normal modes, reaction path vector and curvature vector in terms of generalized adiabatic modes associated with internal parameters that are used to describe the reaction complex. For reaction (1), H tunneling plays a significant role even at room temperature, but does not explain the strongly curved Arrhenius correlations observed experimentally. The probability of H tunneling can be directly related to the curvature of the reaction path and the associated curvature couplings. The reaction is preceeded in the forward and reverse direction by energy-consuming conformational changes that prepare the reactant for the actual 1,2-H shift, which requires only little energy. The effective energy needed for CH bond breaking is just 6,kcal,mol,1 for (1). The gas-phase and the solution-phase mechanisms of (1) differ considerably, which is reflected by the activation enthalpies: 11.4 (gas, calculated) and 4.3,kcal,mol,1 (solution, measured). Stabilizing interactions with solvent molecules take place in the latter case and reduce the importance of H tunneling. The non-linearity of the measured Arrhenius correlations most likely results from bimolecular reactions of the carbene becoming more important at lower temperatures. Copyright © 2002 John Wiley & Sons, Ltd. [source] Soft X-ray radiation-damage studies in PMMA using a cryo-STXMJOURNAL OF SYNCHROTRON RADIATION, Issue 3 2003Tobias Beetz Radiation damage sets a fundamental limit for studies with ionizing radiation; cryo-methods are known to ease these limits. Here, measurements on mass loss and the decrease in the C=O bond density as measured by oxygen-edge XANES (NEXAFS) spectroscopy in thin films of poly(methylmethacrylate) (PMMA), studied in a vacuum, are reported. While cryo-methods allow more than 95% of the mass to remain at doses up to ,Gy, there is little difference in C=O bond density versus dose between 298,K and 113,K sample temperatures. At both temperatures the critical dose for bond breaking is ,15 × 106,Gy. [source] The effect of interstitial hydrogen on the electronic structure of the B2 FeAl alloyPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 10 2007Estela A. González Abstract The electronic structure and bonding in a B2 Fe,Al alloy with and without hydrogen as an interstitial atom were studied within the framework of the density functional theory and the findings compared with previous results in Fe an Al. The hydrogen absorption turns out to be a favorable process. The hydrogen was found near an Al octahedral site, the Al,H distance being shorter than that of Fe,H. The density of states (DOS) curves show several peaks below the d metal band which is made up mostly of hydrogen based states (>50% H1s) while the metal contribution includes mainly s- and p-orbitals. An electron transfer of nearby 0.14 e, comes from the metal to the H. The overlap population values reveal metal,metal bond breaking, the intermetallic bond being the most affected. The H bond mainly with the Al atoms and the reported Fe,H overlap population is much lower than that corresponding to FePd alloys and BCC Fe. The changes in the overlap population show the Fe,Al bond is weakening nearly 53% after H absorption, while the Fe,Fe bond is only weakened 23%. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Ultra-fast dynamics in solids: non-equilibrium behaviour of magnetism and atomic structureANNALEN DER PHYSIK, Issue 7-8 2009K.H. Bennemann Abstract Non-equilibrium physics is of fundamental interest, for example, for extensions of statistical mechanics and thermodynamics. In particular, it is important to understand how conservation laws like energy conservation and angular-momentum conservation in magnetic solids control the time scale of the dynamics. Laser irradiation may cause intense electronic excitations and thus a strong non-equilibrium state. Results are presented for the ultra-fast response of magnetism in ferromagnetic transition metals like Ni, Co, Fe, and Gd and furthermore of the atomic structure in semiconductors like Si, Ge, and InSb. Non-thermal melting is a most spectacular example of ultra-fast bond breaking. Time-resolved magnetooptical experiments yielding sub-picosecond spin dynamics are discussed. The spin dynamics is accompanied by THz light emission. The structural changes in semiconductors, bond changes sp3 , s2p2, and phase transitions occur within about 100 fs. The results also shed light on electron-transfer processes, on ionization, and on molecular dissociation dynamics, which may occur during fs and as times. We discuss the application of time-resolved analysis to tunnelling problems and the phase diagram of high-Tc superconductivity. [source] Ultra-fast dynamics in solids: non-equilibrium behaviour of magnetism and atomic structureANNALEN DER PHYSIK, Issue 7-8 2009K.H. Bennemann Abstract Non-equilibrium physics is of fundamental interest, for example, for extensions of statistical mechanics and thermodynamics. In particular, it is important to understand how conservation laws like energy conservation and angular-momentum conservation in magnetic solids control the time scale of the dynamics. Laser irradiation may cause intense electronic excitations and thus a strong non-equilibrium state. Results are presented for the ultra-fast response of magnetism in ferromagnetic transition metals like Ni, Co, Fe, and Gd and furthermore of the atomic structure in semiconductors like Si, Ge, and InSb. Non-thermal melting is a most spectacular example of ultra-fast bond breaking. Time-resolved magnetooptical experiments yielding sub-picosecond spin dynamics are discussed. The spin dynamics is accompanied by THz light emission. The structural changes in semiconductors, bond changes sp3 , s2p2, and phase transitions occur within about 100 fs. The results also shed light on electron-transfer processes, on ionization, and on molecular dissociation dynamics, which may occur during fs and as times. We discuss the application of time-resolved analysis to tunnelling problems and the phase diagram of high-Tc superconductivity. [source] Comprehensive Analysis of DNA Strand Breaks at the Guanosine Site Induced by Low-Energy Electron AttachmentCHEMPHYSCHEM, Issue 1 2010Jiande Gu Prof. Dr. Abstract To elucidate the role of guanosine in DNA strand breaks caused by low-energy electrons (LEEs), theoretical investigations of the LEE attachment-induced CO ,-bonds and N-glycosidic bond breaking of 2,-deoxyguanosine-3,,5,-diphosphate (3,,5,-dGMP) were performed using the B3LYP/DZP++ approach. The results reveal possible reaction pathways in the gas phase and in aqueous solutions. In the gas phase LEEs could attach to the phosphate group adjacent to the guanosine to form a radical anion. However, the small vertical detachment energy (VDE) of the radical anion of guanosine 3,,5,-diphosphate in the gas phase excludes either CO bond cleavage or N-glycosidic bond breaking. In the presence of the polarizable surroundings, the solvent effects dramatically increase the electron affinities of the 3,,5,-dGDP and the VDE of 3,,5,-dGDP,. Furthermore, the solvent,solute interactions greatly reduce the activation barriers of the CO bond cleavage to 1.06,3.56 kcal,mol,1. These low-energy barriers ensure that either C5,O5, or C3,O3, bond rupture takes place at the guanosine site in DNA single strands. On the other hand, the comparatively high energy barrier of the N-glycosidic bond rupture implies that this reaction pathway is inferior to CO bond cleavage. Qualitative agreement was found between the theoretical sequence of the bond breaking reaction pathways in the PCM model and the ratio for the corresponding bond breaks observed in the experiment of LEE-induced damage in oligonucleotide tetramer CGTA. This concord suggests that the influence of the surroundings in the thin solid film on the LEE-induced DNA damage resembles that of the solvent. [source] Transport Processes at ,-Quartz,Water Interfaces: Insights from First-Principles Molecular Dynamics SimulationsCHEMPHYSCHEM, Issue 7 2008Waheed A. Adeagbo Dr. Abstract Car,Parrinello molecular dynamics (CP,MD) simulations are performed at high temperature and pressure to investigate chemical interactions and transport processes at the ,-quartz,water interface. The model system initially consists of a periodically repeated quartz slab with O-terminated and Si-terminated (1000) surfaces sandwiching a film of liquid water. At a temperature of 1000 K and a pressure of 0.3 GPa, dissociation of H2O molecules into H+ and OH, is observed at the Si-terminated surface. The OH, fragments immediately bind chemically to the Si-terminated surface while Grotthus-type proton diffusion through the water film leads to protonation of the O-terminated surface. Eventually, both surfaces are fully hydroxylated and no further chemical reactions are observed. Due to the confinement between the two hydroxylated quartz surfaces, water diffusion is reduced by about one third in comparison to bulk water. Diffusion properties of dissolved SiO2 present as Si(OH)4 in the water film are also studied. We do not observe strong interactions between the hydroxylated quartz surfaces and the Si(OH)4 molecule as would have been indicated by a substantial lowering of the Si(OH)4 diffusion coefficient along the surface. No spontaneous dissolution of quartz is observed. To study the mechanism of dissolution, constrained CP,MD simulations are done. The associated free energy profile is calculated by thermodynamic integration along the reaction coordinate. Dissolution is a stepwise process in which two SiO bonds are successively broken. Each bond breaking between a silicon atom at the surface and an oxygen atom belonging to the quartz lattice is accompanied by the formation of a new SiO bond between the silicon atom and a water molecule. The latter loses a proton in the process which eventually leads to protonation of the oxygen atom in the cleaved quartz SiO bond. The final solute species is Si(OH)4. [source] | |||||||||||||