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91.
Gaikwad AV Holuigue A Thathagar MB ten Elshof JE Rothenberg G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(24):6908-6913
Leaching of palladium species from Pd nanoparticles under C--C coupling conditions was observed for both Heck and Suzuki reactions by using a special membrane reactor. The membrane allows the passage of palladium atoms and ions, but not of species larger than 5 nm. Three possible mechanistic scenarios for palladium leaching were investigated with the aim of identifying the true catalytic species. Firstly, we examined whether or not palladium(0) atoms could leach from clusters under non-oxidising conditions. By using our membrane reactor, we proved that this indeed happens. We then investigated whether or not small palladium(0) clusters could in fact be the active catalytic species by analysing the reaction composition and the palladium species that diffused through the membrane. Neither TEM nor ICP analysis supported this scenario. Finally, we tested whether or not palladium(II) ions could be leached in the presence of PhI by oxidative addition and the formation of [Pd(II)ArI] complexes. Using mass spectrometry, UV-visible spectroscopy and 13C NMR spectroscopy, we observed and monitored the formation and diffusion of these complexes, which showed that the first and the third mechanistic scenarios were both possible, and were likely to occur simultaneously. Based on these findings, we maintain that palladium nanoparticles are not the true catalysts in C--C coupling reactions. Instead, catalysis is carried out by either palladium(0) atoms or palladium(II) ions that leach into solution. 相似文献
92.
Chandra S Kumar A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(3-4):697-701
Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from pyrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies .The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Co(L1)2(NO3)2 and Ni(L1)2(NO3)2 complexes which are 1:2 electrolytes. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except Co(L1)2(NO3)2 and Ni(L1)2(NO3)2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes. 相似文献
93.
Samik Gupta Anil Kumar Barik Sachindranath Pal Arijit Hazra Somnath Roy Ray J. Butcher Susanta Kumar Kar 《Polyhedron》2007
Four cis-dioxomolybdenum complexes of general formula [MoO2(Ln)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L4)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh3. The complexes are characterized by elemental analysis, electronic spectra, IR, 1H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO5 donor environment. 相似文献
94.
95.
Anil Kumar Bidhan C. Saha Ali A. Khan Vijay Kumar Sunil K. Verma Krishna K. Prasad 《International journal of quantum chemistry》1999,73(3):307-316
Total quenching of the low‐Rydberg state of Na in collision with thermal Ne and Ar was investigated, for the first time, employing a molecular approach in the impact parameter formalism. A large basis set of Slater‐type orbitals was used to calculate the molecular structure of the transient quasimolecule formed during the collision; pseudopotentials were used to incorporate the effective binding of the distant electron. A 14‐channel calculation was carried out to evaluate the total depopulation cross sections for Na(9s) colliding with the ground‐state Ne and Ar atoms in the thermal‐energy region. The two colliding pairs not only differ from each other, but also show wide variations from the previously studied Na He pair, in terms of details of the collision dynamics. In the case of the Na Ar system, a unique feature that leads to appreciably larger quenching cross sections shows qualitative agreement with the measurement. A comparative study of three (He/Ne/Ar Na) colliding pairs reveals that the simplified approach like the free‐electron model or the impulse approximation fails to provide details of such state‐changing reactions. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 73: 307–316, 1999 相似文献
96.
Photocleavable protecting groups are important in synthesis and caging. Among many such groups, 2-nitrobenzyl and related groups have been found useful in many applications. However, most of the known 2-nitrobenzyl-based caging chromophores show either low quantum yield or the photolysis wavelength is not suitable for various applications. In this paper, we report 2-nitro-3-naphthalenemethanol (NNM) as an efficient photocleavable protecting group for molecules containing a carboxylic function. NNM possesses photochemical properties better than the 2-nitrobenzyl chromophores as it is photoactivatable at 380 nm in aqueous medium (CH3CN/H2O, 3:2 v/v) showing the desired photochemistry. The carboxylic acids are efficiently photoreleased from NNM-based esters in almost quantitative yield. 相似文献
97.
Balaban TS Linke-Schaetzel M Bhise AD Vanthuyne N Roussel C Anson CE Buth G Eichhöfer A Foster K Garab G Gliemann H Goddard R Javorfi T Powell AK Rösner H Schimmel T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2267-2275
We report two crystal structures of a synthetic porphyrin molecule which was programmed for self-assembly. The same groups which ensure that bacteriochlorophylls c, d, and e can self-assemble into the chlorosomal nanorods, the photosynthetic antenna system of some green bacteria, have been engineered into desired positions of the tetrapyrrolic macrocycle. In the case of the 5,15-meso-substituted anchoring groups, depending upon the concentration, by using the same crystallization solvents, either a tetragonal or a layered structure of porphyrin stacks were encountered. Surprisingly, pi-pi interactions combined with extensive dispersive interactions, which also encompass cyclohexane, one of the crystallization solvents, win over putative hydrogen bonding. We are aware that our compounds differ considerably from the natural bacteriochlorophylls, but based upon our findings, we now question the hydrogen-bonding network, previously proposed to organize stacks of bacteriochlorophylls. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) on various isomeric compounds support our challenge of current models for the chlorosomal antenna as these show structures, astonishingly similar to those of chlorosomes. 相似文献
98.
N. S. Rathore Anil Kumar Pabby A. K. Venugopalan 《Journal of Radioanalytical and Nuclear Chemistry》2005,262(3):543-549
Hydrated iron oxide or amorphous-Fe2O3·3.5 H2O (HFeO), hydrated titanium oxide (HTiO) and hydrated thorium oxide (HThO) were synthesized and their applicability for the decontamination of intermediate level liquid wastes (ILLW) was tested. The sorption of a few actinides like plutonium and americium on HFeO, 137Cs and 106Ru on HTiO and 90Sr on HThO was investigated as a function of pH, time and loading capacity of the hydrous oxide with metal ions. The influence of the total dissolved salt content was also monitored. Some of these parameters influenced the sorption behavior significantly. The radiation stability of these inorganic sorbents were studied by irradiating them up to 48 Mrad. Adsorbed actinides and fission products were successfully eluted from HFeO and from the mix-bed of HTiO and HThO by 0.5M nitric acid.The authors wish to thank Shri R. D. Changarani, Chief Superintendent NRG Facilities and Shri P. K. Dey, Head FRD for their valuable advice and constant support. 相似文献
99.
Anil Kumar 《Journal of Chemical Sciences》1986,97(1):1-7
The distribution of nickel and cobalt species has been computed, based on the pH-dependent model of Zirino and Yamamoto. The
media used in the pH range of 7 to 9 are natural waters like fresh water, sea water and a mixture of them at different compositions,
at 25°C temperature and 1 atm pressure. In fresh water, both nickel and cobalt dominate as free cations at lower pH, and as
carbonato complexes at higher pH. In sea water, chloro complexes are significant. In mixtures of the two kinds of water, as
might be found in a totally mixed estuary, chloro complexes are important, varying slowly with pH. Sea water plays an important
role in complexation. The present results are in excellent agreement with experimental data obtained by the resin exchange
method. 相似文献
100.
Pritam Dolui Vikas Tiwari Parul Saini Dr. Tarak Karmakar Koushik Makhal Harshita Goel Dr. Anil J. Elias 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202200829
An efficient, metal-free, catalyst-free and solvent-free methodology for the reductive amination of levulinic acid with different anilines has been developed using HBpin as the reducing reagent. This protocol offers an excellent method to avoid solvents and added catalysts on the synthesis of different kinds of N-substituted pyrrolidones under metal free conditions. It is also the first report for the synthesis of different pyrrolidones by solvent-free as well as catalyst-free methods. The proposed mechanism for the formation of pyrrolidone has been supported by DFT calculations and control experiments. 相似文献