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141.
The Synthesis of some 4-Nitroisoxazoles from Pseudonitrosites of Chalcones The action of dinitrogen trioxide with α,β-unsaturated ketones of the chalcone type leads to pseudonitrosites (Table 1) which are cyclized to 4-nitro-3,5-diarylisoxazoles (Table 2). 相似文献
142.
Polleux L Labbé E Buriez O Périchon J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4678-4686
The electrochemical behaviour of CoBr(2)bpy (bpy=2,2'-bipyridine) catalyst precursor in acetonitrile has been studied, revealing its possible reduction into the corresponding Co(I) and Co(0) complexes. These low-valent cobalt species appear to be stable on the time scale of cyclic voltammetry. In the presence of aromatic halides, both complexes undergo oxidative addition, the latter Co(0) species allowing the activation of poorly reactive aromatic chlorides. The arylcobalt(III) and arylcobalt(II) obtained are reduced at the same potential as the original Co(II) and Co(I) complexes, respectively, resulting in the observation of overall ECE mechanisms in both cases. The electrochemical study shows that vinylic acetates competitively react with electrogenerated Co(0) species, leading to a labile complex. Preparative scale electrolyses carried out from solutions containing aromatic halides (ArX), vinyl acetate (vinylOAc) and a catalytic amount of CoBr(2)bpy lead to a mixture of biaryl (Ar-Ar) and arene (ArH) as long as the potential is set on the plateau of the Co(II) right arrow over left arrow Co(I) reduction wave. The coupling product (Ar-vinyl) is formed only if the electrolysis is performed on the plateau of the Co(I)/Co(0) reduction wave. A mechanism is proposed for the overall cobalt-catalyzed coupling reaction between aromatic halides and allylic acetates. 相似文献
143.
Walrand J Lengelé M Blanquet G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(14):3299-3303
Using diode-laser spectroscopy, the intensities of 58 lines of the v(1) + v(1/2) - v(1/2) band and 36 lines of the 2v(1) - v(1) band of OCS have been measured. The corresponding band strengths S(0)(v) and the vibrational transition dipoles micro(v) have been derived through least squares fitting of these individual intensities. The band strengths values have been determined with a precision better than 2.5%. 相似文献
144.
Jacques Barrau Ghassoub Rima Tajani El Amraoui 《Journal of organometallic chemistry》1998,570(2):8645
The reactions of the divalent species (ArO)2M (Ar=2,4,6-[(CH3)2NCH2]3C6H2; M=Ge, Sn) with either Me3SiN3, elemental S8, Se or transition metal complexes M′(CO)n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph3P)2Pt·C2H4 have resulted in the isolation of either the new stable formal metallanimines (ArO)2M=N–SiMe3, germanethione, -selone (ArO)2Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)2M=M′(CO)n, (ArO)2M=Pt(PPh3)2 complexes, respectively. The direct oxidation of the (ArO)2M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)2M–O–]2. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)2Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)2M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione. 相似文献
145.
Alemani D Chopard B Galceran J Buffle J 《Physical chemistry chemical physics : PCCP》2005,7(18):3331-3341
A new approach to numerically solve a reaction-diffusion system is given, specifically developed for complex systems including many reacting/diffusing species with broad ranges of rate constants and diffusion coefficients, as well as complicated geometry of reacting interfaces. The approach combines a Lattice Boltzmann (LB) method with a splitting time technique. In the present work, the proposed approach is tested by focusing on the typical reaction process between a metal ion M and a ligand L, to form a complex ML with M being consumed at an electrode. The aim of the paper is to systematically study the convergence conditions of the associated numerical scheme. We find that the combination of LB with the time splitting method allows us to solve the problem for any value of association and dissociation rate constant of the reaction process. Also, the method can be extended to a mixture of ligands. We stress two main points: (1) the LB approach is particularly convenient for the flux computation of M and (2) the splitting time procedure is very well suited for reaction processes involving association-dissociation rate constants varying on many orders of magnitude. 相似文献
146.
Rodeschini V Van de Weghe P Salomon E Tarnus C Eustache J 《The Journal of organic chemistry》2005,70(6):2409-2412
[reaction: see text] Enantioselective deprotonation of 4-substituted cyclohexanones and highly stereoselective conjugate addition of higher order mixed cuprates were the key steps in a concise synthesis of fumagalone-related molecules. The origin of the (low) biological activity of the new compounds as compared to fumagalone is briefly discussed. 相似文献
147.
A single crystal of a new sodium calcium iron (III) phosphate, Na4CaFe4(PO4)6, has been synthesized by a flux method and characterized by X-ray diffraction, Mössbauer spectroscopy and magnetic susceptibility measurements. The compound crystallizes in the monoclinic space group C2/c(a=12.099(5) Å, b=12.480(5) Å, c=6.404(2) Å, β=113.77(3)°, Z=2, R1=0.022, Rw2=0.066). The crystal structure belongs to the alluaudite type, characterized by the X(2)X(1)M(1)M(2)2(PO4)3 general formula. The open framework results from Fe2O10 units of edge-sharing FeO6 octahedra, which alternate with M(1)O6 octahedra (M(1)=Na+Ca) that form infinite chains. These chains are linked together through the common corners of PO4 tetrahedra yielding two distinct tunnels of sodium cation occupation. This compound is antiferromagnetic with a Néel temperature of 35 K. Mössbauer parameters are consistent with the structural results. 相似文献
148.
Chardon-Noblat S Horner O Chabut B Avenier F Debaecker N Jones P Pécaut J Dubois L Jeandey C Oddou JL Deronzier A Latour JM 《Inorganic chemistry》2004,43(5):1638-1648
Reaction of the unsymmetrical phenol ligand 2-((bis(2-pyridylmethyl)amino)methyl)-6-(((2-pyridylmethyl)benzylamino)methyl)-4-methylphenol (HL-Bn) or its 2,6-dichlorobenzyl analogue (HL-BnCl(2)) with Fe(H(2)O)(6)(ClO(4))(2) in the presence of disodium m-phenylenedipropionate (Na(2)(mpdp)) followed by exposure to atmosphere affords the diiron(II,III) complexes [Fe(2)(L-Bn)(mpdp)(H(2)O)](ClO(4))(2) and [Fe(2)(L-BnCl(2))(mpdp)(CH(3)OH)](ClO(4))(2), respectively. The latter complex has been characterized by X-ray crystallography. It crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.3095(14) A, b = 20.1073(19) A, c = 19.4997(19) A, alpha = 90 degrees, beta = 94.471(2) degrees, gamma = 90 degrees, V = 5202.6(9) A(3), and Z = 4. The structure of the compound is very similar to that of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) determined earlier, except for the replacement of a water by a methanol on the ferrous site. Magnetic measurements of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) reveal that the two high-spin Fe ions are moderately antiferromagnetically coupled (J = -3.2(2) cm(-)(1)). Upon dissolution in acetonitrile the terminal ligand on the ferrous site is replaced by a solvent molecule. The acetonitrile-water exchange has been investigated by various spectroscopic techniques (UV-visible, NMR, M?ssbauer) and electrochemistry. The substitution of acetonitrile by water is clearly evidenced by M?ssbauer spectroscopy by a reduction of the quadrupole splitting value from 3.14 to 2.41 mm/s. In addition, it causes a 210 mV downshift of the oxidation potential of the ferrous site and a similar reduction of the stability domain of the mixed-valence state. Exhaustive electrolysis of a solution of [Fe(2)(L-Bn)(mpdp)(H(2)O)](2+) shows that the aqua diferric species is not stable and undergoes a chemical reaction which can be partly reversed by reduction to the mixed-valent state. This and other electrochemical observations suggest that upon oxidation of the diiron center to the diferric state the aqua ligand is deprotonated to a hydroxo. This hypothesis is supported by M?ssbauer spectroscopy. Indeed, this species possesses a large quadrupole splitting value (DeltaE(Q) >or= 1.0 mm.s(-)(1)) similar to that of analogous complexes with a terminal phenolate ligand. This study illustrates the drastic effects of aqua ligand exchange and deprotonation on the electronic structure and redox potentials of diiron centers. 相似文献
149.
A new ternary ruthenium oxide Na(2)RuO(4) was prepared and shown to crystallize with a new structure type. Single crystal X-ray diffraction measurements reveal that Na(2)RuO(4) consists of RuO(4) chains made up of RuO(5) trigonal bipyramids by sharing axial corners. Na(2)RuO(4) is a magnetic semiconductor with a variable range hopping behavior, and its molar magnetic susceptibility chi(mol) has a broad maximum at approximately 74 K. The derivative d(chi(mol).T)/dT exhibits a peak at 37.7 K which has been confirmed by heat capacity measurement to be due to long-range antiferromagnetic ordering. 相似文献
150.
A generalized fractional programming problem is specified as a nonlinear program where a nonlinear function defined as the maximum over several ratios of functions is to be minimized on a feasible domain of
n
. The purpose of this paper is to outline basic approaches and basic types of algorithms available to deal with this problem and to review their convergence analysis. The conclusion includes results and comments on the numerical efficiency of these algorithms.This research was supported by NSERC (grant A8312) and Cooperation franco-québécoise (projet 20-02-13). Paper presented at Workshop on Mathematical Programming Catholic University of Rio de Janeiro, Brazil, October 10–14, 1988. 相似文献