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11.
Vera P. Shmachkova Nina S. Kotsarenko Vladislav V. Kanazhevskiy Galina N. Kryukova Dimitri I. Kochubey Jacques Vedrine 《Reaction Kinetics and Catalysis Letters》2007,91(1):177-185
Methods of the preparation of catalysts for alkane skeletal isomerization based on uniform nanoparticles of sulfated zirconia
anchored to different supports were investigated. These catalysts were characterized by using the ICP, HRTEM and BET techniques.
The activities of the catalysts in the reaction of n-butane isomerization were measured and compared with those of bulk catalysts. 相似文献
12.
Summary The aquation kinetics ofcis-[Co(NH3)Br(en)2]2+ were studied in aqueous and mixed aqueous-nonaqueous solvents in the presence of KBr, KCl, LiCl, NaNO3 and NaClO4 as supporting electrolytes. It was found that the association between the complex ion and Cl–, Br– and NO
3
–
ions takes place. The association constants, KIP, were evaluated from kinetic measurements. The kinetic parameters in the studied media are related to the influence of the cosolvents on the solvation spheres of the reactants and activated complex. 相似文献
13.
The three-dimensional structures of a number of [M(SR)(4)](n-) complexes, where M is a 3d transition metal and R is an alkyl or aryl group, have been analyzed using density functional theory (DFT). Special attention is paid to the Fe(II)/Fe(III) mimics of rubredoxin. The Fe(II) model complex [Fe(SCH(3))(4)](2-) has an equilibrium conformation with D2d symmetry. The DFT energy has been decomposed into contributions for ligand-ligand and metal-ligand interactions. The latter contribution is analyzed with the angular overlap model (AOM) and constitutes the dominant stereospecific interaction in the Fe(II) complex. The sulfur lone-pair electrons exert anisotropic pi interactions on the 3d(6) shell of Fe(II), which are controlled by the torsion angles, omega(i), for the rotations of the S(i)-C(beta) bonds around the Fe-S(i) axes. In contrast, the pi interactions acting on the high-spin 3d(5) shell of Fe(III) are isotropic. As a consequence, the stereochemistry of the Fe(III) complexes is determined by the Coulomb repulsions between the ligands and has S(4) symmetry. The electrostatic repulsions between the lone pairs of the sulfurs are an essential component of the ligand-ligand interaction. The lone-pair repulsions distort the 90 degree angle SFeS' angles (delta + delta(t)) and give rise to a correlation between delta and omega, which is confirmed by crystallographic data. Both the Fe(II) and Fe(III) complexes exhibit structural bistability due to the presence of low-lying equilibrium conformations with S(4) symmetry in which the complex can be trapped by the crystalline host. 相似文献
14.
Ekaterina A. Martynova Vladislav A. Voloshkin Sbastien G. Guillet Francis Bru Marek Beli Kristof Van Hecke Catherine S. J. Cazin Steven P. Nolan 《Chemical science》2022,13(23):6852
We present the use of gold sensitizers [Au(SIPr)(Cbz)] (PhotAu 1) and [Au(IPr)(Cbz)] (PhotAu 2) as attractive alternatives to state-of-the-art iridium-based systems. These novel photocatalysts are deployed in [2 + 2] cycloadditions of diallyl ethers and N-tosylamides. The reactions proceed in short reaction times and in environmentally friendly solvents. [Au(SIPr)Cbz] and [Au(IPr)(Cbz)] have higher triplet energy (ET) values (66.6 and 66.3 kcal mol−1, respectively) compared to commonly used iridium photosensitizers. These ET values permit the use of these gold complexes as sensitizers enabling energy transfer catalysis involving unprotected indole derivatives, a substrate class previously inaccessible with state-of-the-art Ir photocatalysts. The photosynthesis of unprotected tetracyclic spiroindolines via intramolecular [2 + 2] cycloaddition using our simple mononuclear gold sensitizer is readily achieved. Mechanistic studies support the involvement of triplet–triplet energy transfer (TTEnT) for both [2 + 2] photocycloadditions.We present the use of gold sensitizers [Au(SIPr)(Cbz)] (PhotAu 1) and [Au(IPr)(Cbz)] (PhotAu 2) as attractive alternatives to state-of-the-art iridium-based systems. 相似文献
15.
Manqi Ruan Hang Zhao Gang Li Chengdong Fu Zhigang Wang Xinchou Lou Dan Yu Vincent Boudry Henri Videau Vladislav Balagura Jean-Claude Brient Peizhu Lai Chia-Ming Kuo Bo Liu Fenfen An Chunhui Chen Soeren Prell Bo Li Imad Laketineh 《The European Physical Journal C - Particles and Fields》2018,78(5):426
After the Higgs discovery, precise measurements of the Higgs properties and the electroweak observables become vital for the experimental particle physics. A powerful Higgs/Z factory, the Circular Electron Positron Collider (CEPC) is proposed. The Particle Flow oriented detector design is proposed to the CEPC and a Particle Flow algorithm, Arbor is optimized accordingly. We summarize the physics object reconstruction performance of the Particle Flow oriented detector design with Arbor algorithm and conclude that this combination fulfills the physics requirement of CEPC. 相似文献
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18.
Dr. Zhenghai Yang Dr. Srinivas Doddipatla Dr. Chao He Vladislav S. Krasnoukhov Prof. Dr. Valeriy N. Azyazov Prof. Dr. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13584-13589
The silene molecule (H2SiCH2; X1A1) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH4). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH2SiH3; X2A′) complex followed by hydrogen migration to the methylsilyl radical (SiH2CH3; X2A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H2SiCH2; X1A1). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level. 相似文献
19.
20.
Novel types of hydrazinopeptide-like units containing five elements of diversity have been prepared in two steps using sequential
Ugi reactions. 相似文献