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991.
Zorica D. Petrovi? Vladimir P. Petrovi? Dušica Simijonovi? Svetlana Markovi? 《Journal of organometallic chemistry》2009,694(24):3852-1017
A set of reactions of different activated olefins and aryl iodides with the trans-dichlorobis(diethanolamine-N)palladium(II) complex (trans-[PdCl2(DEA)2]) as a precatalyst was performed, in the presence of diethanolamine (DEA) as a weak base, and NaOEt as a strong base. It was established that the presence of NaOEt slightly lowered the yields, but significantly accelerated the reactions. This experimental finding is in agreement with our computational investigation that shows that significantly higher activation barrier is required for the preactivation reaction in the presence of a weak base than in the presence of a strong base. The reaction between the catalytically active DEA-Pd(0)-Cl complex, formed in the preactivation reaction, and iodobenzene was investigated using density functional theory. Two mechanisms for the oxidative addition of the activated complex were found. The first mechanism is based on a nucleophilic attack of Pd on I of iodobenzene, and yields an intermediate tetracoordinated Pd complex (aI2). The second mechanism begins with a nucleophilic attack of Pd on the benzene ring, and yields a tricoordinated intermediate complex (bI4). It was concluded, on the basis of structural and energetical properties of aI2 and bI4, that the second mechanism is significantly more favorable. It was shown that the oxidative addition requires noticeable lower activation energy than that required for the preactivation process. Thus, our investigations indicate that oxidative addition is not the rate determining step for the Heck reactions investigated in this work, but preactivation step. 相似文献
992.
Surfactant-free fabrication of Cu2O nanosheets from Cu colloids and their tunable optical properties
Novel sheetlike Cu2O two-dimensional (2D) nanoarchitectures were successfully synthesized via a copper nanoparticle-mediated process for the first time. Uniform and nearly monodisperse Cu nanocolloids were firstly synthesized by disproportionating reaction of Cu+ at the surfactant-free ambient conditions, and Cu2O nanosheets were subsequently synthesized by choosing ethanol solvent agent to limit the oxidized processes of Cu nanocolloids. The synthesized products were systematically studied by X-ray powder diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-vis absorption spectra. It was demonstrated that the solvent agent of ethanol played key roles in the formation of the as-synthesized nanosheets. By choosing the different solvent agents to limit the oxidized processes, Cu2O nanospheres and nanocubes can be selectively synthesized accordingly. 相似文献
993.
S. Cordier F. Dorson F. Grasset Y. Molard B. Fabre H. Haneda T. Sasaki M. Mortier S. Ababou-Girard C. Perrin 《Journal of Cluster Science》2009,20(1):9-21
In this contribution, we present a review of our recent works about the design of phosphor nanoparticles and materials based
on [Mo6X14]2− cluster units (X = Cl, Br, I) as well as the functionalization of monocrystalline Si(111) surfaces by Mo6 clusters. Our purpose was to use the specific properties of cluster units found in inorganic solids for the design of new
nanomaterials with potential applications in nanotechnologies (e.g. phosphor dyes for bio labelling, light emitting diodes,
redox active molecular junctions…) using soft chemistry techniques. Phosphor Cs2Mo6X14@SiO2 nanoparticles emitting in 550–900 nm upon photo-excitation were synthesised using a ‘water in oil’ microemulsion technique.
They exhibit a regular shape (~45 nm) and are based on [Mo6X14]2− cluster units and Cs+ counter cations embedded in a silica matrix. ((n–C4H9)4N)2Mo6Br14@ZnO colloids and nanopowders are based on the association of ZnO crystalline nano-particles with Mo6 cluster units adsorbed on their surface. They exhibit a large emission window in the visible region that can be tuned by
modulation of the excitation wave length in order to selectively obtain the emission of either clusters units or ZnO nanocrystals
or of both entities. Functionalized surfaces were obtained by the attachment of cluster units on a Si(111) surface through
pyridine end capped organic chains using a multi-step procedure. Modified surfaces were characterized by X-ray photoemission
spectroscopy (XPS), atomic force microscopy (AFM), IR and electrochemical analysis. The surface coverage can be modulated
by the controlled introduction of inert organic chains among pyridine end-capped ones before the cluster anchoring step. 相似文献
994.
Reduction of aromatic compounds (A) is achieved in the presence of alkyl halides RX (X = I or Br) at Ag–Pd electrodes in organic solvents. Those electrodes allow the one-electron reduction of RX with the selective formation of free radicals R. This new process (heterogeneous one-electron catalysis, H1EC) was used to alkylate in situ arenes. This mode of alkylation leads to re-visit previous results concerning redox catalysis published by Henning Lund when more conventional electrodes (like glassy carbon or mercury) were used and afforded similar results within a totally different potential scale. These preliminary results underline the reactivity differences between the molecular electrode (A−) and the almost ideal catalysis process (facile and specific liberation of free alkyl radicals). 相似文献
995.
996.
Young Eun Cheon Myunghyun Paik Suh Prof. 《Angewandte Chemie (International ed. in English)》2009,48(16):2899-2903
Quick on the uptake : Palladium nanoparticles were fabricated simply by immersing {[Zn3(ntb)2(EtOH)2]?4 EtOH}n ( 1 ) in an MeCN solution of Pd(NO3)2 at room temperature, without any extra reducing agent. 3 wt % PdNPs@[ 1 ]0.54+(NO3?)0.54 significantly increase H2 uptake capacities, both at 77 K and 1 bar and at 298 K and high pressures (see picture, red curve) compared to [Zn3(ntb)2]n (black). ntb=4,4′,4′′‐nitrilotrisbenzoate.
997.
Kersten M. Gericke Dr. David I. Chai Nikolas Bieler Dr. Mark Lautens Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(8):1447-1451
Shall we dance? Within the proposed mechanism for the palladium‐catalyzed title reaction, the strained alkene norbornene (or norbornadiene) enters and exits the catalytic cycle in a catalytic “square dance”, acting as both a promoter and a coupling partner in the formation of four carbon–carbon bonds, two of them by challenging C? H activation processes.
998.
Michael G. Organ Prof. Selçuk Çalimsiz Dr. Mahmoud Sayah Ka Hou Hoi Alan J. Lough Dr. 《Angewandte Chemie (International ed. in English)》2009,48(13):2383-2387
Incredible Bulk : A series of N‐heterocyclic carbene catalysts (see picture) were prepared and evaluated in the Suzuki–Miyaura reaction. A variety of sterically encumbered tetra‐ortho‐substituted biaryl products were formed from unreactive aryl chlorides using the isopentyl‐substituted catalyst at temperatures ranging from 65 °C to room temperature. The cyclopentyl‐substituted catalyst was virtually inactive, demonstrating that “flexible bulk” is essential to promote these transformations.
999.
Anne Brennführer Helfried Neumann Dr. Matthias Beller Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(23):4114-4133
A CO group richer : (Hetero)arenes are vital intermediates in the manufacture of agrochemicals, dyes, pharmaceuticals, and other industrial products. In the past decades transition‐metal‐catalyzed coupling reactions of aryl halides with all types of nucleophiles have been developed. This Review summarizes recent work in the area of palladium‐catalyzed carbonylation reactions of aryl halides and related compounds (see scheme).
1000.
Xiao Chen Dr. Keary M. Engle Dong‐Hui Wang Jin‐Quan Yu Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(28):5094-5115
Pick your Pd partners : A number of catalytic systems have been developed for palladium‐catalyzed C? H activation/C? C bond formation. Recent studies concerning the palladium(II)‐catalyzed coupling of C? H bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed.