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101.
Manirul?IslamEmail author Dildar?Hossain Paramita?Mondal Kazi?Tuhina Anupam?Singha?Roy Sanchita?Mondal Manir?Mobarak 《Transition Metal Chemistry》2011,36(2):223-230
A thiosemicarbazone Cu(II) complex anchored to a polystyrene framework has been synthesized and characterized by analytical
and spectroscopic techniques. The complex was found to be a highly active catalyst for the oxidation of various organic substrates
including alkenes and alcohols using H2O2 as oxidant. The reaction conditions were optimized with respect to temperature, solvent, oxidant, catalyst amount, and substrate
to peroxide ratio. The heterogeneous catalyst was reused five times without significant loss of activity. A comparison between
the catalytic activities of this polymer-supported Cu(II) complex and its homogeneous analogue was carried out. 相似文献
102.
Phase diagram, crystal chemistry and thermoelectric properties of compounds in the Ca-Co-Zn-O system
W. Wong-Ng T. Luo W.H. Tang Q. Huang S. Chattopadhyay T. Tritt 《Journal of solid state chemistry》2011,184(8):2159-2166
In the Ca-Co-Zn-O system, we have determined the tie-line relationships and the thermoelectric properties, solid solution limits, and structures of two low-dimensional cobaltite series, Ca3(Co, Zn)4O9−z and Ca3(Co,Zn)2O6−z at 885 °C in air. In Ca3(Co,Zn)4O9−z, which has a misfit layered structure, Zn was found to substitute in the Co site to a limit of Ca3(Co3.8Zn0.2)O9−z. The compound Ca3(Co,Zn)2O6−z (n=1 member of the homologous series, Can+2(Co,Zn)n(Co,Zn)′O3n+3−z) consists of one-dimensional parallel (Co,Zn)2O66− chains that are built from successive alternating face-sharing (Co,Zn)O6 trigonal prisms and ‘n’ units of (Co,Zn)O6 octahedra along the hexagonal c-axis. Zn substitutes in the Co site of Ca3Co2O6 to a small amount of approximately Ca3(Co1.95Zn0.05)O6−z. In the ZnO-CoOz system, Zn substitutes in the tetrahedral Co site of Co3O4 to the maximum amount of (Co2.49Zn0.51)O4−z and Co substitutes in the Zn site of ZnO to (Zn0.94Co0.06)O. The crystal structures of (Co2.7Zn0.3)O4−z, (Zn0.94Co0.06)O, and Ca3(Co1.95 Zn0.05)O6−z are described. Despite the Ca3(Co, Zn)2O6−z series having reasonably high Seebeck coefficients and relatively low thermal conductivity, the electrical resistivity values of its members are too high to achieve high figure of merit, ZT. 相似文献
103.
Mukherjee A Dateer RB Chaudhuri R Bhunia S Karad SN Liu RS 《Journal of the American Chemical Society》2011,133(39):15372-15375
We report two viable routes for the 1,2-difunctionalization of aminoalkynes using only oxidants. In the presence of a gold catalyst, nitrones enable the oxoamination of aminoalkynes 1 to form 2-aminoamides 2. With a suitable gold catalyst, nitrosobenzenes implement an alkyne/nitroso metathesis of the same substrates to give 2-oxoiminylamides 3. These two novel oxidations also provide 1,2-aminoalcohols with opposite regioselectivity via NaBH(4) reduction in situ. 相似文献
104.
Bhowmik P Nayek HP Corbella M Aliaga-Alcalde N Chattopadhyay S 《Dalton transactions (Cambridge, England : 2003)》2011,40(31):7916-7926
Three manganese(III) compounds, [Mn(III)(vanoph)(DMF)(H(2)O)]ClO(4) (1), [Mn(III)(vanoph)(N(3))(H(2)O)]·2H(2)O (2) and [Mn(III)(saloph)(μ(1,3)-N(3))](n) (3), where H(2)vanoph = N,N'-(1,2-phenylene)-bis(3-methoxysalicylideneimine), H(2)saloph = N,N'-(1,2-phenylene)-bis(salicylideneamine) are tetradentate N(2)O(2) ligands and DMF = N,N-dimethylformamide, have been prepared and characterised by elemental analysis, IR and UV-Vis spectroscopy and single-crystal X-ray diffraction studies. Compounds 1 and 2 are monomeric but compound 3 consists of a chain system with the repeating unit [Mn(III)(saloph)(N(3))] bridged by μ-1,3 azide. Compound 1 crystallises in monoclinic space group P2(1)/n with cell dimensions of a = 11.1430(2), b = 16.3594(3), c = 15.4001(3) ?, β = 108.417(1), Z = 4 whereas compounds 2 and 3 crystallise in orthorhombic space groups Pbca and Pna2(1), respectively, with cell dimensions of a = 16.069(3), b = 15.616(3), c = 18.099(4) ?, Z = 8 (for 2) and a = 18.760(9), b = 13.356(5), c = 6.616(3) ?, Z = 4 (for 3). In all the compounds, Mn(III) has a six-coordinated pseudo-octahedral geometry in which O(2), O(3), N(1) and N(2) atoms of the deprotonated di-Schiff base constitute the equatorial plane. In both compounds 1 and 2, water molecules are present in the fifth coordination sites in the apical positions. The sixth coordination sites are occupied by one O atom of a solvent DMF in compound 1 and an N atom of azide in compound 2. The coordinated water initiates hydrogen-bonded networks in both compounds 1 and 2 to form well-isolated supramolecular dimers. At room temperature the χ(M)T values for the compounds 1 and 2 remain almost constant until 30 K. Below this temperature, the χ(M)T values drastically drop to 0.72 cm(3) mol(-1) K for 1 and 0.52 cm(3) mol(-1) K for 2. The best fits were obtained with J = -0.92 cm(-1), |D| = 2.05 cm(-1), g = 2.0 and R = 8.1 × 10(-4) for 1 and J = -1.16 cm(-1), |D| = 2.05 cm(-1), g = 2.0 and R = 1.2 × 10(-3) for 2. However, in compound 3, two axial positions are occupied by the azide ions. The Mn···Mn repeating distance is 6.616 ? along the chain. Magnetic characterisation shows that the μ(1,3)-bridging azide ion mainly transmits an antiferromagnetic interaction (J = -6.36 cm(-1)) between Mn(III) ions. The presence of two methoxy groups increases the steric crowding in the H(2)vanoph moiety and thereby inhibits the formation of a polynuclear compound with this ligand. 相似文献
105.
Intramolecular cycloaddition of the syn- and the anti-nitrone 9 and 13 leads stereoselectively to the azabicyclic compounds 10 and 14 which may provide access to both enantiomers of the quinolizidine alkaloid lasubine II. 相似文献
106.
107.
Geiger RA Leto DF Chattopadhyay S Dorlet P Anxolabéhère-Mallart E Jackson TA 《Inorganic chemistry》2011,50(20):10190-10203
Three peroxomanganese(III) complexes [Mn(III)(O(2))(mL(5)(2))](+), [Mn(III)(O(2))(imL(5)(2))](+), and [Mn(III)(O(2))(N4py)](+) supported by pentadentate ligands (mL(5)(2) = N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine, imL(5)(2) = N-methyl-N,N',N'-tris((1-methyl-4-imidazolyl)methyl)ethane-1,2-diamine, and N4py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) were generated by treating Mn(II) precursors with H(2)O(2) or KO(2). Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature, variable-field MCD data demonstrate that these complexes have very similar electronic transition energies and ground-state zero-field splitting parameters, indicative of nearly identical coordination geometries. Because of uncertainty in peroxo (side-on η(2) versus end-on η(1)) and ligand (pentadentate versus tetradentate) binding modes, density functional theory (DFT) computations were used to distinguish between three possible structures: pentadentate ligand binding with (i) a side-on peroxo and (ii) an end-on peroxo, and (iii) tetradentate ligand binding with a side-on peroxo. Regardless of the supporting ligand, isomers with a side-on peroxo and the supporting ligand bound in a tetradentate fashion were identified as most stable by >20 kcal/mol. Spectroscopic parameters computed by time-dependent (TD) DFT and multireference SORCI methods provided validation of these isomers on the basis of experimental data. Hexacoordination is thus strongly preferred for peroxomanganese(III) adducts, and dissociation of a pyridine (mL(5)(2) and N4py) or imidazole (imL(5)(2)) arm is thermodynamically favored. In contrast, DFT computations for models of [Fe(III)(O(2))(mL(5)(2))](+) demonstrate that pyridine dissociation is not favorable; instead a seven-coordinate ferric center is preferred. These different results are attributed to the electronic configurations of the metal centers (high spin d(5) and d(4) for Fe(III) and Mn(III), respectively), which results in population of a metal-peroxo σ-antibonding molecular orbital and, consequently, longer M-O(peroxo) bonds for peroxoiron(III) species. 相似文献
108.
Halder A Bhatt S Nayak SK Chattopadhyay S Bhattacharya S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,84(1):25-31
The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C(60) and C(70) with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo-p-tert-butylcalix[8]arene (1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1. The most fascinating feature of the present study is that 1 binds selectively C(60) compared to C(70) as obtained from binding constant (K) data of C(60)-1 (K(C60-1)) and C(70)-1 (K(C70-1)) complexes which are enumerated to be 265,000 dm(3) mol(-1) and 63,43 dm(3) mol(-1), respectively, and selectivity in binding (K(C60-1)/K(C70-1)) is estimated to be 4.18 as obtained from UV-Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C(60)-1 and C(70)-1 complexes are estimated to be 80,760 and 68,780 dm(3) mol(-1), respectively, with selectivity in binding (K(C60-1)/K(C70-1)) ~1.18. (1)H NMR analysis provides very good support in favor of strong binding between C(60) and 1. The high value of K value for C(60)-1 complex indicates that 1 forms an inclusion complex with C(60). 相似文献
109.
Ray A Chattopadhyay S Bhattacharya S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1435-1442
The photo-physical aspects of non-covalently linked assemblies of a series of fullerenes, namely, C60, C70, tert-butyl-(1,2-methanofullerene)-61-carboxylate (1) and [6,6]-phenyl C70 butyric acid methyl ester (2) with a designed zinc phthalocyanine (ZnPc), viz., zinc-1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (3) in toluene medium are studied employing absorption spectrophotometric, steady state and time resolved fluorescence spectroscopic measurements. Of central interest in these investigations is the preferential binding of various fullerenes with ZnPc in toluene. The ground state interaction between fullerenes and 3 is first evidenced from UV-Vis measurements. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 3 in presence of both underivatized and derivatized fullerenes. K values for the complexes of C60, C70, 1 and 2 with 3 are determined to be 6500, 22,230, 47,800 and 54,770 dm3 mol(-1), respectively. The magnitude of K suggests that 3 preferentially binds C70 and derivatized C70 in comparison to C60 and 1. Time resolved emission measurements establish that C(70)-3 and 2-3 complexes are stabilized much more in comparison to C(60)-3 and 1-3 systems in terms of charge separation process. Semi empirical calculations employing third parametric method substantiate the strong binding of C70 and its derivative with 3 in terms of heat of formation values of the respective complexes, and at the same time, determine the orientation of bound guest (here fullerenes) with the molecular plane of 3. 相似文献
110.