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1.
Ilya I. Moiseev Tatiana A. Stromnova Irina N. Busygina Natalya Yu. Tihonova Natalya Yu. Kozitsyna Arkady M. Ellern Mikhail Yu. Antipin Yury T. Struchkov 《Journal of Cluster Science》1992,3(4):411-421
Thermolysis of tetranuclear palladium clusters Pd4(-Q)4 Pd4(-Q)4(-O2CR)4 (Q=CPh2 or CO;R=Me, CMe3, Ph, CH2Cl or CF3) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO2 insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)2(PPh3)]2 with HCO2H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh3 ligand to the palladium atom. The structure of the complex formed, [Pd(-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis. 相似文献
2.
Kozitsyna N. Yu. Martens M. V. Stolyarov I. P. Gekhman A. E. Vargaftik M. N. Moiseev I. I. 《Russian Chemical Bulletin》1999,48(9):1673-1681
The effects of the solvent and the ligand chirality on the regioselectivity of oxidative esterification of propylene and cyclohexene
by PdII carboxylates were studied using achiral (MeCO2
−, Me2CHCH2CO2
−), racemic ((±)-CF3CF2CF2OC*F(CF3)CO2
−), and chiral ((S)−(+)−MeC*H(Et)CO2
−, (+)−CF3CF2CF2OC*F(CF3)CO2
−) carboxylate ligands. The oxidation of alkenes in aprotic media (CHCl3, CH2Cl2, CO2, THF) affords mainly allylic esters (in the case of cyclohexene also homoallylic esters) and the oxidative esterification
at the vinylic position is absent. In weakly solvating media (CHCl3, CH2Cl2) the regioselectivity of cyclohexene oxidation (the allyl to homoallyl ratio) increases substantially on going from achiral
or racemic acido ligands to chiral acido ligands. In a more donor medium (THF) the ligand chirality effect almost vanishes.
The effects of the ligand chirality and the nature of the solvent on the mechanism of alkene oxidation by PdII complexes are discussed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1695–1703, September, 1999. 相似文献
3.
N. S. Akhmadullina N. V. Cherkashina N. Yu. Kozitsyna A. E. Gekhman M. N. Vargaftik 《Kinetics and Catalysis》2009,50(3):396-400
The kinetics of reactions of palladium(II) acetate with cobalt(II), nickel(II), and copper(II) acetates were studied by spectrophotometry. These reactions produce heterobimetallic complexes PdII(μ-OOCMe)4MII(OH2)(HOOCMe)2, where M = Co, Ni, or Cu. These reactions are very slow in carefully dehydrated (<0.01% H2O) acetic acid, but are considerably enhanced by water or acetonitrile. Our data indicate that the activation of the kinetically inert ring structure of the initial palladium complex Pd3(μ-OOCMe)6 by means of the nucleophilic attack of an H2O or acetonitrile molecule is the key step of the reaction mechanism. 相似文献
4.
A. A. Veligzhanin Ya. V. Zubavichus N. Yu. Kozitsyna V. Yu. Murzin E. V. Khramov A. A. Chernyshov 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2013,7(3):422-433
The formation of metal or metal-oxide nanoparticles from four different precursor systems, including palladium(II) acetate, zinc(II) acetate, their 1: 1 mechanical mixture and the palladium-zinc bimetallic acetate complex PdZn(OCOMe)4(H2O), upon heating in a He + 5% H2 atmosphere is studied using the X-ray diffraction and EXAFS (Extended X-ray absorption fine structure) techniques in the in situ mode. X-ray diffraction is primarily used to monitor changes in the phase composition of the samples. At specific moments when qualitative changes in the composition occur, EXAFS spectra at the K-edges of Pd and Zn are also measured. Using a combination of these two techniques, a detailed sequence of the phase transformations in each of the four precursor systems is revealed. It is found that the bimetallic acetate complex and the mixture of two monometallic acetates undergo chemical reduction to form zerovalent palladium under milder conditions than zinc acetate. However, the formation of a PdZn alloy from the mixture of metal acetates proceeds with a significant diffusion barrier. 相似文献
5.
I. P. Stolarov Zh. V. Dobrokhotova G. N. Kryukova N. Yu. Kozitsyna A. E. Gekhman M. N. Vargaftik I. I. Moiseev 《Russian Chemical Bulletin》2005,54(3):803-806
An unusual for Pd catalysts dehydration of α-alkyl and α, α′-dialkylbenzyl alcohols PhCR′R″OH (R′ = H, Me, Et, Bu; R″ = H, Me) occurs in the presence of the palladium(I) cluster [Pd4(CO)4(OAc)4] (1) in an inert atmosphere to form ethers PhCR′R″-O-CR′ R″ and water. The catalyst is an intermediate of cluster 1 reduction to Pd black, while neither the starting cluster 1, nor Pd black, which is the decomposition product, are active in the catalysis of this reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 788–791, March, 2005. 相似文献
6.
N. Yu. Kozitsyna S. E. Nefedov N. V. Cherkashina V. N. Ikorskii M. N. Vargaftik I. I. Moiseev 《Russian Chemical Bulletin》2005,54(9):2215-2218
The first heterometallic palladium(II) acetate complex with divalent 3d metal, PdCo(μ-OOCMe)4(NCMe)·3 MeCN, was synthesized and structurally characterized.
Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2149–2152, September, 2005. 相似文献
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9.
N. Yu. Kozitsyna L. M. Dikareva V. I. Andrianov S. V. Zinchenko V. A. Khutoryanskii F. K. Shmidt M. A. Porai-Koshits I. I. Moiseev 《Russian Chemical Bulletin》1988,37(8):1695-1698
Conclusions A novel type of platinum-palladium heteronuclear complex containing bridging acetate ligands, namely, (3-allyl)palladium(II)triacetatotriphenylphosphine) platinum(II), has been prepared by reaction of bis[3-allyl)chloropalladium] with triacetatoargento(I)triphenyl-phosphineplatinum(II); the complex was characterized on the basis of x-ray structural analysis, and its IR, PMR, and31P-NMR spectral data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1894–1897, August, 1988. 相似文献
10.
A. V. Chistyakov M. V. Tsodikov V. Yu. Murzin F. A. Yandieva Ya. V. Zubavichus N. Yu. Kozitsyna A. E. Gekhman V. V. Kriventsov I. I. Moiseev 《Kinetics and Catalysis》2011,52(2):258-272
The results of the direct conversion of ethanol and its mixture with glycerol into a C4–C10+ alkane and olefin fraction in the presence of Pd-, Zn-, and Pd-Zn-containing catalysts, which were prepared by supporting
homo- and heterometallic acetate complexes onto the surface of γ-Al2O3, are reported. It was found that, in the presence of mono- and bicomponent Pd-ZnO (Pd; ZnO)/γ-Al2O3 systems, selectivity in the formation of alkanes, olefins, or their mixtures in the target fraction can be controlled as
a result of the cocatalytic effect of active components that are responsible for the catalyst activity in condensation and
hydrogenation reactions. The structures of the active components were studied and the genesis of the catalytic systems was
characterized using XAFS, XPS, and XRD analysis. It was found that the addition of glycerol considerably increased the yield
of the target hydrocarbon fraction. 相似文献