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11.
Mechanistic Insights into the Pd‐Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer‐Sphere Mechanism Involving a Palladium Hydride Intermediate
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Supaporn Sawadjoon Dr. Per J. R. Sjöberg Dr. Andreas Orthaber Prof. Olle Matsson Dr. Joseph S. M. Samec 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1520-1524
The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π‐allylpalladium intermediate. A second‐order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI‐MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O–H bond and C–O bond cleavages are involved in rate‐determining steps. A stereochemical study supports an outer‐sphere nucleophilic attack of the π‐allylpalladium intermediate giving complete chiral transfer from starting material to product. 相似文献
12.
Consider a Poisson process X in R d with density 1. We connect each point of X to its k nearest neighbors by undirected edges. The number k is the parameter in this model. We show that, for k = 1, no percolation occurs in any dimension, while, for k = 2, percolation occurs when the dimension is sufficiently large. We also show that if percolation occurs, then there is exactly one infinite cluster. Another percolation model is obtained by putting balls of radius zero around each point of X and let the radii grow linearly in time until they hit another ball. We show that this model exists and that there is no percolation in the limiting configuration. Finally we discuss some general properties of percolation models where balls placed at Poisson points are not allowed to overlap (but are allowed to be tangent). © 1996 John Wiley & Sons, Inc. 相似文献
13.
Youjun He Yi Zhou Guangjin Zhao Jie Min Xia Guo Bo Zhang Maojie Zhang Jing Zhang Yongfang Li Fengling Zhang Olle Inganäs 《Journal of polymer science. Part A, Polymer chemistry》2010,48(8):1822-1829
A new benzodithiophene (BDT)‐based polymer, poly(4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene vinylene) (PBDTV), was synthesized by Pd‐catalyzed Stille‐coupling method. The polymer is soluble in common organic solvents and possesses high thermal stability. PBDTV film shows a broad absorption band covering from 350 nm to 618 nm, strong photoluminescence peaked at 545 nm and high hole mobility of 4.84 × 10?3 cm2/Vs. Photovoltaic properties of PBDTV were studied by fabricating the polymer solar cells based on PBDTV as donor and PC70BM as acceptor. With the weight ratio of PBDTV: PC70BM of 1:4 and the active layer thickness of 65 nm, the power conversion efficiency of the device reached 2.63% with Voc = 0.71 V, Isc = 6.46 mA/cm2, and FF = 0.57 under the illumination of AM1.5, 100 mW/cm2. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1822–1829, 2010 相似文献
14.
Olle Häggström 《Journal of statistical physics》1996,84(5-6):1351-1361
We study the random-cluster model on a homogeneous tree, and show that the following three conditions are equivalent for a random-cluster measure: quasilocality, almost sure quasilocality, and the almost sure nonexistence of infinite clusters. As a consequence of this, we find that the plus measure for the Ising model on a tree at sufficiently low temperatures can be mapped, via a local stochastic transformation, into a measure which fails to be almost surely quasilocal. 相似文献
15.
The kinetics and mechanism of the aromatic nucleophilic substitution reaction of 2,4-dinitrochlorobenzene (DNCB) with OH- in nonionic sugar-derived micelles were investigated and compared with those for reaction in polyoxyethylene glycol surfactants. Hydroxyl groups on the sugar headgroups of micellized n-nonyl beta-D-glucopyranoside (C9G1), n-dodecyl beta-D-maltoside (C12G2), and n-dodecyl beta-D-maltotrioside (C12G3) are partially deprotonated by OH- and the alkoxide ions react with DNCB, forming an arene ether. Observation of more than one isosbestic point indicates that more than one intermediate ether is formed, largely at C3 or C4 with micellar stereocontrol. Over time the ethers react with OH- giving 2,4-dinitrophenoxide ion. 相似文献
16.
Price WS Stilbs P Söderman O 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,160(2):139-143
The influence of finite length gradient pulses on NMR diffusion experiments on liquids confined to diffuse between two parallel planes is investigated. It is experimentally verified that the pore size decreases when determined using finite gradient pulses if the results are analyzed within the short gradient pulse approximation. The results are analyzed using the matrix formulation. The observed minima in the echo decay profiles are considerably less sharp than theoretical analysis would indicate and we suggest that this is due to the presence of a distribution of pore sizes in the sample. In addition, effects due to the presence of background gradients are discussed. It is argued that effects due to the finite length gradient pulses are relatively minor and in realistic applications the effects due to inhomogeneities in pore sizes and effects due to background gradients will constitute more serious problems in pore size determinations by means of NMR diffusometry. 相似文献
17.
Hagslätt H Jönsson B Nydén M Söderman O 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,161(2):138-147
Pulsed field gradient NMR diffusometry is a promising tool for investigating structures of porous material through determinations of dynamic displacements of molecules in porous systems. A problem with this approach is the lack of closed analytical expressions for echo-decays in anything but idealized pore geometries. We present here an approach based on calculating the appropriate diffusion propagator by means of finite element calculations. The suggested method is quite general, and can be applied to arbitrary porous systems. The protocol for the calculations is outlined and we show results from some different cases: diffusion in confined geometries and in systems that are spatially inhomogeneous with respect to concentration. 相似文献
18.
Martin Sahlberg Premysl Beran Thomas Kollin Nielsen Yngve Cerenius Krisztina Kads Marko P.J. Punkkinen Levente Vitos Olle Eriksson Torben R. Jensen Yvonne Andersson 《Journal of solid state chemistry》2009,182(11):3113-3117
A novel aluminium rich alloy for hydrogen storage has been discovered, ScAl0.8Mg0.2, which has very promising properties regarding hydrogen storage capacity, kinetics and stability towards air oxidation in comparison to hydrogen absorption in state-of-the-art intermetallic compounds. The absorption of hydrogen was found to be very fast, even without adding any catalyst, and reversible. The discovered alloy crystallizes in a CsCl-type structure, but decomposes to ScH2 and Al(Mg) during hydrogen absorption. Detailed analysis of the hydrogen absorption in ScAl0.8Mg0.2 has been performed using in situ synchrotron radiation powder X-ray diffraction, neutron powder diffraction and quantum mechanical calculations. The results from theory and experiments are in good agreement with each other. 相似文献
19.
Bhandary S Ghosh S Herper H Wende H Eriksson O Sanyal B 《Physical review letters》2011,107(25):257202
One of the primary objectives in molecular nanospintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this Letter, we demonstrate by first principles density functional calculations, as well as second order perturbation theory, that a strain induced change of the spin state, from S=1→S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in the sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP in different spin states, each with a unique saturation moment and easy axis orientation. The effect is brought about by a change in Fe-N bond length in FeP, which influences the molecular level diagram as well as the interaction between the C atoms of the graphene layer and the molecular orbitals of FeP. 相似文献
20.
Olle Hggstrm 《Random Structures and Algorithms》2001,18(3):267-278
We construct a coupling of two distinct Gibbs measures for Markov random fields with the same specifications, such that the existence of an infinite path of disagreements between the two configurations has probability 0. This shows that the independence assumption in the disagreement percolation method for proving Gibbsian uniqueness cannot be dropped without being replaced by other conditions. A similar counterexample is given for couplings of Markov chains. © 2001 John Wiley & Sons, Inc. Random Struct. Alg., 18, 267–278, 2001 相似文献