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31.
32.
Mayilmurugan R Harum BN Volpe M Sax AF Palaniandavar M Mösch-Zanetti NC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):704-713
The asymmetric molybdenum(VI) dioxo complexes of the bis(phenolate) ligands 1,4‐bis(2‐hydroxybenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐methylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐di‐tert‐butylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐flurobenzyl)‐1,4‐diazepane, and 1,4‐bis(2‐hydroxy‐4‐chlorobenzyl)‐1,4‐diazepane (H2(L1)–H2(L6), respectively) have been isolated and studied as functional models for molybdenum oxotransferase enzymes. These complexes have been characterized as asymmetric complexes of type [MoO2(L)] 1–6 by using NMR spectroscopy, mass spectrometry, elemental analysis, and electrochemical methods. The molecular structures of [MoO2(L)] 1–4 have been successfully determined by single‐crystal X‐ray diffraction analyses, which show them to exhibit a distorted octahedral coordination geometry around molybdenum(VI) in an asymmetrical cis‐β configuration. The Mo? Ooxo bond lengths differ only by ≈0.01 Å. Complexes 1 , 2 , 5 , and 6 exhibit two successive MoVI/MoV (E1/2, ?1.141 to ?1.848 V) and MoV/MoIV (E1/2, ?1.531 to ?2.114 V) redox processes. However, only the MoVI/MoV redox couple was observed for 3 and 4 , suggesting that the subsequent reduction of the molybdenum(V) species is difficult. Complexes 1 , 2 , 5 , and 6 elicit efficient catalytic oxygen‐atom transfer (OAT) from dimethylsulfoxide (DMSO) to PMe3 at 65 °C at a significantly faster rate than the symmetric molybdenum(VI) complexes of the analogous linear bis(phenolate) ligands known so far to exhibit OAT reactions at a higher temperature (130 °C). However, complexes 3 and 4 fail to perform the OAT reaction from DMSO to PMe3 at 65 °C. DFT/B3LYP calculations on the OAT mechanism reveal a strong trans effect. 相似文献
33.
Ramasamy K Mazumdar D Zhou Z Wang YH Gupta A 《Journal of the American Chemical Society》2011,133(51):20716-20719
Nanocrystals and nanoclusters of the room-temperature magnetic spinel CuCr(2)S(4) have been synthesized using a facile solution-based method. The synthesis involves hot injection of an excess of 1-dodecanethiol (1-DDT) into a boiling coordinating solvent containing CuCl(2) and CrCl(3)·6H(2)O. Using octadecylamine (ODA) as a solvent yields cube-shaped nanocrystals with an average size of 20 ± 2 nm, while with oleylamine (OLA), nanoclusters with an average size of 31 ± 2.5 nm are obtained. In both cases, powder X-ray diffraction patterns confirmed the formation of the pure spinel phase without any impurities. While the synthesized powders are superparamagnetic near room temperature, they exhibit ferromagnetic behavior at lower temperatures, with magnetization (M(S)) values of 30 emu/g (1.63 μ(B)/f.u.) and 33 emu/g (1.79 μ(B)/f.u.) for the ODA- and OLA-capped nanocrystals and nanoclusters, respectively, at 5 K. 相似文献
34.
Balamurugan M Mayilmurugan R Suresh E Palaniandavar M 《Dalton transactions (Cambridge, England : 2003)》2011,40(37):9413-9424
Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) ?) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) ?) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) ?) is shorter than the Ni-N(py) bond (2.074(4) ?) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed. 相似文献
35.
A.S Haja Hameed A Nixon Azariah P Ramasamy 《Journal of Physics and Chemistry of Solids》2003,64(1):147-153
The metastable zone width for the solution of organic nonlinear material: indole-3-aldehyde (IA) has been determined for the various solvents of acetone, methanol and ethyl acetate and the corresponding IA crystals have been grown by temperature lowering technique. The surface analysis on different planes of the grown crystals has been carried out. The range of transmission and powder second harmonic generation efficiency of IA have been reported. 相似文献
36.
Surendran Ramasamy Abdul Rahman Mohamed Subhash Bhatia 《Reaction Kinetics and Catalysis Letters》2002,75(2):353-358
Oxidative coupling of methane for the production of ethylene was studied over Li-Ni/MgO catalyst in a fixed bed reactor. The influences of important reaction parameters such as temperature (T), methane/oxygen ratio (CH4/O2) in feed and space velocity of reactants (V/mcat) were studied over the conversion of methane, yields of ethylene and ethane and selectivity of ethylene formation. The reaction conditions were varied as 650 < T < 850oC, 0.83 x 10-6 < V/mcat < 2.92 x 10-6 m3/g s and 1 < CH4/O2 ratio < 8. 相似文献
37.
The influence of concentration, ageing and pH of the gel medium on the periodic precipitation of cobalt oxinate in agar gel
is reported. The results are explained on the basis of Shinohara’s revised flocculation theory. The flocculation value (F) increases with increase in the gel concentration whereas it decreases with increase in ageing and pH of the gel. The raise
in temperature of the gel increases the solubility of the sparingly soluble substance and hence theF value. The effect of additives on the periodic precipitation of cobalt (II) oxinate is reported. 相似文献
38.
A comparative study of the Chevrel phases Mo6S8, Mo6Se8, PbMo6S8 and Cu1.8Mo6S8 is made by the positron angular correlation technique at room temperature. Electronic properties like the number of conduction electrons per cluster, the density of states at the Fermi level, the electron effective masses and the Fermi velocities are obtained within the framework of the free electron model. The results are discussed in terms of available theoretical and other experimental data. 相似文献
39.
Anamalai K. Samylingam L. Kadirgama K. Samykano M. Najafi G. Ramasamy D. Rahman M. M. 《Journal of Thermal Analysis and Calorimetry》2019,135(2):1533-1544
Journal of Thermal Analysis and Calorimetry - The emphasis of this paper is to evaluate the thermophysical properties of crystalline nanocellulose (CNC)-based nanofluid and the optimized machining... 相似文献
40.
Potassium hydrogen malate monohydrate (PHMM), a semi-organic nonlinear optical material, has been synthesized and single crystals were grown from aqueous solution. Single crystals of PHMM have been grown by slow evaporation of solvent at room temperature up to dimensions of 22 mm×16 mm×14 mm. Single-crystal X-ray diffraction study on grown crystals shows that they belong to monoclinic system and non-centrosymmetry spacegroup Cc. The structural perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. Fourier transform infrared (FTIR) spectroscopic study was performed for the identification of different modes of functional groups present in the compound. The UV–Vis transmission spectrum has been recorded in the range 200–1100 nm. The thermal stability of the compound has been determined by TG-DTA curves. The dielectric studies were performed. From the microhardness measurements, Vicker's hardness number (Hv), Stiffness constant (C11), fracture toughness (kc), Brittle index (Bi) and yield strength (σy) have been calculated. The Young's modulus was calculated using the Knoop hardness measurement. The SHG relative efficiency of PHMM crystal was found to be 1.2 times higher than that of KDP. 相似文献