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1.
A. R. Kudinov L. S. Shul'pina P. V. Petrovskii M. I. Rybinskaya 《Russian Chemical Bulletin》1992,41(3):549-554
Interaction of [Ru(-C
6
H
6
)Cl
2
]
2
with indenyl- or fluorenyllithium in THF gives, together with cationic benzene complexes [Ru(
5
-C
9
H
7
)(-C
6
H
6
)]+ and [Ru(
5
-C
13
H
9
)(-C
6
H
6
)]+, the neutral cyclohexadienyl derivatives Ru(
5
-C
9
H
6
-C
9
H
7
) and Ru(
5
-C
13
H
9
)(
5
-C
6
H
6
-C
13
H
9
), respectively. Interaction of the cyclohexadienyl complexes with Al
2
O
3
, Ph
3
C+, and CF
3
CO
2
H has been studied. Reaction of Ru(
5
-C
13
H
9
)(
5
-C
6
H
7
) with CF
3
CO
2
H in the presence of an arene yields cationic cyclohexadienylarene complexes: [Ru(
5
-C
13
H
9
)(
6
-arene)]+ (arene=C
6
H
6
or 1,3,5-Me
3
C
6
H
3
).A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 699–706, March, 1992. 相似文献
2.
Computer simulations based on Discrete Element Method have been performed in order to investigate the influence of interparticle interactions on the kinetics of self-assembly and the mechanical strength of nanoparticle aggregates.Three different systems have been considered.In the first system the interaction between particles has been simulated using the JKR (Johnson,Kendall and Roberts) contact theory,while in the second and third systems the interaction between particles has been simulated using van der Waals and electrostatic forces respectively.In order to compare the mechanical behaviour of the three systems,the magnitude of the maximum attractive force between particles has been kept the same in all cases.However,the relationship between force and separation distance differs from case to case and thus,the range of the interparticle force.The results clearly indicate that as the range of the interparticle force increases,the self-assembly process is faster and the work required to produce the mechanical failure of the assemblies increases by more than one order of magnitude. 相似文献
3.
[(-ArH)Fe(-C5H5)]+BF4
–, where ArH is benzene or toluene, catalyzes the photochemical oxidation of hydrocarbons by oxygen in acetonitrile. Cyclohexane and ethylbenzene are oxidized to the alcohol and ketone derivatives, which are formed in different amounts (after gas-liquid chromatography); benzaldehyde is obtained from styrene. The proposed mechanism involves the formation of a peroxide radical from the organometallic complex, which is capable of hydrogen atom abstraction from the alkane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1680–1683, July, 1991. 相似文献
4.
Georgiy B. Shul'pin Yuriy N. Kozlov Lidia S. Shul'pina Armando J.L. Pombeiro 《Tetrahedron》2012,68(41):8589-8599
Oxone (peroxysulphate) very efficiently oxidizes benzene to p-quinone (TON 1140) and alkanes to the corresponding alcohols and ketones (aldehydes) in aqueous acetonitrile 50 °C if catalytic amounts of complex [Mn2L2O3]2+ (L=1,4,7-trimethyl-1,4,7-triazacyclononane) and oxalic acid are present in the solution. In contrast to the similar reaction with H2O2, the alkane oxidation with Oxone does not afford the corresponding alkyl hydroperoxides. Phenol was quantitatively oxidized to a mixture of p-quinone and pyrocatechol (9:1 ratio). Cyclohexanol gave cyclohexanone (TON 400). The proposed mechanism includes the formation of an oxidizing species containing the Mn(V)O fragment. A kinetic study demonstrated that an adduct of [Mn2L2O3]2+ and oxalic acid is formed in the initial stage. This adduct reacts with Oxone to generate the oxidizing species. 相似文献
5.
Cage‐like Copper(II) Silsesquioxanes: Transmetalation Reactions and Structural,Quantum Chemical,and Catalytic Studies 下载免费PDF全文
Dr. Alexey N. Bilyachenko Dr. Marina S. Dronova Alexey I. Yalymov Dr. Frédéric Lamaty Dr. Xavier Bantreil Prof. Jean Martinez Christelle Bizet Lidia S. Shul'pina Prof. Alexander A. Korlyukov Dmitry E. Arkhipov Dr. Mikhail M. Levitsky Prof. Elena S. Shubina Dr. Alexander M. Kirillov Prof. Georgiy B. Shul'pin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(24):8758-8770
The transmetalation of bimetallic copper–sodium silsesquioxane cages, namely, [(PhSiO1.5)10(CuO)2(NaO0.5)2] (“Cooling Tower”; 1 ), [(PhSiO1.5)12(CuO)4(NaO0.5)4] (“Globule”; 2 ), and [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (“Sandwich”; 3 ), resulted in the generation of three types of hexanuclear cylinder‐like copper silsesqui‐ oxanes, [(PhSiO1.5)12(CuO)6(C4H9OH)2(C2H5OH)6] ( 4 ), [(PhSiO1.5)12(CuO)6(C4H8O2)4(PhCN)2(MeOH)4] ( 5 ), and [(PhSiO1.5)12(CuO)6(NaCl)(C4H8O2)12(H2O)2] ( 6 ). The products show a prominent “solvating system–structure” dependency, as determined by X‐ray diffraction. Topological analysis of cages 1 – 6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1 , 2 , and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols. 相似文献
6.
Alexey N. Bilyachenko Mikhail M. Levitsky Alexey I. Yalymov Alexander A. Korlyukov Viktor N. Khrustalev Anna V. Vologzhanina Lidia S. Shul'pina Nikolay S. Ikonnikov Alexander E. Trigub Pavel V. Dorovatovskii Xavier Bantreil Frdric Lamaty Jrme Long Joulia Larionova Igor E. Golub Elena S. Shubina Georgiy B. Shul'pin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(49):15586-15589
A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe6O19} core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]5. This structural organization induces antiferromagnetic interactions between the FeIII ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols. 相似文献
7.
This paper addresses the use of different slotted pores in rotating membrane emulsification technology.Pores of square and rectangular shapes were studied to understand the effect of aspect ratio (1-3.5) and their orientation on oil droplet formation.Increasing the membrane rotation speed decreased the droplet size,and the oil droplets produced were more uniform using slotted pores as compared to circular geometry.At a given rotation speed,the droplet size was mainly determined by the pore size and the fluid velocity of oil through the pore (pore fluid velocity).The ratio of droplet diameter to the equivalent diameter of the slotted pore increased with the pore fluid velocity.At a given pore fluid velocity and rotation speed,pore orientation significantly influences the droplet formation rate: horizontally disposed pores (with their longer side perpendicular to the membrane axis) generate droplets at double the rate of vertically disposed pores.This work indicates practical benefits in the use of slotted membranes over conventional methods. 相似文献
8.
A methodology is proposed for predicting the effective thermal conductivity of dilute suspensions of nanoparticles (nanofluids) based on rheology.The methodology uses the rheological data to infer microstructures of nanoparticles quantitatively,which is then incorporated into the conventional Hamilton-Crosser equation to predict the effective thermal conductivity of nanofluids.The methodology is experimentally validated using four types of nanofluids made of titania nanoparticles and titanate nanotubes dispersed in water and ethylene glycol.And the modified Hamilton-Crosser equation successfully predicted the effective thermal conductivity of the nanofluids. 相似文献
9.
Bo Xiao a Qingchun Yuan b a EaStChem School of Chemistry Purdie Building North Haugh University of St. rews Fife St. rews KY ST UK b Institute of Particle Science Engineering School of Processing Environmental & Mineral Engineering University of Leeds Houldworth Building Leeds LS JT UK 《中国颗粒学报》2009,7(2)
Hydrogen is expected to play an important role in future transportation as a promising alternative clean energy source to carbon-based fuels.One of the key challenges to commercialize hydrogen energy is to develop appropriate onboard hydrogen storage systems,capable of charging and discharging large quantities of hydrogen with fast enough kinetics to meet commercial requirements.Metal organic framework (MOF) is a new type of inorganic and organic hybrid nanoporous particulate materials.Its diverse networks can enhance hydrogen storage through tuning the structure and property of MOFs.The MOF materials so far developed adsorb hydrogen through weak disperston interactions,which allow significant quantity of hydrogen to be stored at cryogenic temperatures with fast kinetics.Novel MOFs are being developed to strengthen the interactions between hydrogen and MOFs in order to store hydrogen under ambient conditions.This review surveys the development of such candidate materials,their performance and future research needs. 相似文献
10.
A. R. Kudinov D. A. Loginov S. N. Ashikhmin A. A. Fil'chikov L. s. Shul'pina P. V. Petrovskii 《Russian Chemical Bulletin》2000,49(9):1637-1639
30-Electron triple-decker complexes [(η-C5H5)Fe(μ-η:η-C4Me4P)Fe(η-C5Me5)]PF6 and [(η-C4Me4)Co(μ-η:η-C4Me4P)Fe(η-C5Me5)]PF6 with a central tetramethylphospholyl ligand were synthesized by stacking reactions of cationic fragments [(η-C5H5)Fe]+ and [(η-C4Me4)Co]+ with nonamethylphosphaferrocene (η-C4Me4P)Fe(η-C5Me5).
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1647–1649, September, 2000. 相似文献