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221.
Damla Durak Anıl Delikanlı Cahit Demetgül İbrahim Kani Selahattin Serin 《Transition Metal Chemistry》2013,38(2):199-206
An unsymmetrical tetradentate Schiff base (H2L) was synthesized by the reaction of 3-methoxysalicylaldehyde, o-phenylenediamine, and salicylaldehyde in EtOH. H2L was characterized by single-crystallographic X-ray analysis. Its Co(II) and Mn(III) complexes ([CoL] and [MnLCl]) were prepared and immobilized on 3-aminopropyltriethoxysilane functionalized silica gel. The immobilized materials were found to be efficient catalysts for epoxidation of styrene in the presence of tert-BuOOH in acetonitrile at 40 °C. The catalysts can be reused several times without significant loss of performance. 相似文献
222.
E. Manuela Garrido Josél Costa Lima Cristina M. Delerue-matos Ana Maria Oliveira Brett 《International journal of environmental analytical chemistry》2013,93(1-2):149-157
Abstract Cyclic, differential pulse and square wave voltammetry were applied to develop an electroanalytical procedure for the determination of a group of herbicides used to treat rice crops: molinate, bensul-ruron-methyl, mefenacet and thiobencarb. The oxidation mechanism causes adsorption problems and consequent poisoning of the electrode surface by the products of the electrochemical reaction. Parameters such as pH, frequency and electrochemical electrode surface treatment were optimized. The analytical methodology developed using square wave voltammetry was applied to the determination of molinate and bensulfuron-methyl in simple or mixed commercial products. 相似文献
223.
Dr. Matthieu Autillo Md. Ashraful Islam Julie Héron Laetitia Guérin Dr. Eleonor Acher Dr. Christelle Tamain Dr. Marie-Claire Illy Dr. Philippe Moisy Dr. Eric Colineau Dr. Jean-Christophe Griveau Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(24):7138-7153
Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center. 相似文献
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226.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling
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Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
227.
Truong Son Pham Katalin Gönczi György Kardos Krisztina Süle László Hegedűs Mihály Kállay Miklós Kubinyi Pál Szabó Imre Petneházy László Tőke Zsuzsa Jászay 《Tetrahedron: Asymmetry》2013,24(24):1605-1614
Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation. 相似文献
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229.
János B. Czirok Ákos Tarcsay Pál D. Mezei András Simon László Balázs 《Supramolecular chemistry》2013,25(10-12):722-728
The size limit of substituents allowing O-through-the-annulus rotation of substituted calix[4]arenes was further extended to the propargyloxy group in 24-propargyloxy-25,26,27-tris(N,N-dimethylcarbamoylmethoxy)-p-tert-butylcalix[4]arene by demonstrating its free but slow motion affording equilibrium between the partial cone and 1,2-alternate conformers. The effect of solvent and upper rim substituents R1 on the conformational inversion was investigated by means of 1H NMR. The rotational isomerisation of the parent (R1 = H) analogue could not unambiguously be detected. The experimental results were supported by comprehensive density functional theory studies. 相似文献
230.
Thomas Courant Valrie Gaëlle Roullin Cyril Cadiou Maït Callewaert Marie Christine Andry Christophe Portefaix Christine Hoeffel Marie Christine deGoltstein Marc Port Sophie Laurent Luce Vander Elst Robert Muller Michaël Molinari Franoise Chuburu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2012,124(36):9253-9256