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131.
研究了无水硫化钠与对二氯苯(以N-甲基吡咯烷酮为溶剂)合成聚苯硫醚反应的宏观动力学,该反应是一个小分子缩合串联自缩聚的过程,通过测定不同反应聚合体系中氯化钠的徨成率和硫化内的转化率,建立了该反应的宏观动力学方程:1/(1-PNaCl+PNa2s)=C0Kt+1;并计算得到220、250℃的表观反应速率为4.5×10^-4和3.0×10^-3kg/(mol.s),表观活化能为134kJ/mol。 相似文献
132.
E. N. Deryagina E. N. Sukhomazova E. P. Levanova 《Chemistry of Heterocyclic Compounds》2002,38(1):40-45
The effect of methanol and ethanol on the route of the gas-phase reaction of 2-chlorothiophene with hydrogen sulfide, leading to 2-thiophenethiol and to bis(2-thienyl) sulfide, has been investigated. It was found that methanol significantly enhances this reaction and increases its selectivity for the thiol at higher temperatures than without the initiator. The optimal conditions were achieved at 570°C in the presence of 10 mole % of methanol when the conversion of the 2-chlorothiophene in the reaction with hydrogen sulfide reaches 98% and the yield of the thiophenethiol (43%) exceeds that of the bis(2-thienyl)sulfide (31%). In the absence of methanol the 2-thiophenethiol is formed only at 510-540°C in just 17% yield, the basic reaction product being the indicated sulfide (52% yield); the conversion of the 2-chlorothiophene does not exceed 54%. 相似文献
133.
O. LeynaudA. Lafond Y. MoëloP. Palvadeau A. Meerschaut 《Journal of solid state chemistry》2002,168(1):41-51
Crystal structures of two new misfit compounds, [SrGd0.5S1.5]1.16NbS2 and [Sr(Fe,Nb)0.5S1.5]1.13NbS2, were determined through the composite approach, i.e., by refining each subpart (Q, H-parts, and the common part) of these composite materials, separately. The Q-part is a three-atom-thick layer, with the NaCl-type structure, where external SrS planes enclose the inner GdS or (Fe,Nb)S plane; the structural difference between these two compounds lies in the central layer within the Q-part: Gd and S atoms are in special positions (octahedral coordination), while Fe and S atoms are statistically distributed on split (×4) positions (tetrahedral coordination) around a central unique site (=special position occupied by Nb). The H-part is a sandwich of sulfur planes enclosing the inner Nb plane as observed for the structure of the binary compound NbS2 itself. The Sr-Gd derivative shows a paramagnetic behavior in the whole studied temperature range (2-300 K). On the other hand, antiferromagnetic interactions occur in the Sr-Fe derivative; the complex magnetic behavior of this compound is related to the statistical distribution of Fe atoms which leads to frustration of the magnetic interactions. At room temperature, experimental values obtained from Mössbauer spectrum correspond to Fe3+ in tetrahedral sulfur environment: isomer shift δ=0.32 mm s−1, and quadrupole splitting ΔE=0.48 mm s−1. 相似文献
134.
Qiang Xu Prof. Dr. Nobuko Tsumori Prof. Dr. Ling Jiang Masanobu Kondo Ryuichi Arakawa Prof. Dr. 《化学:亚洲杂志》2007,2(5):599-608
Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)2(SO3F)3]? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and 13C and 15N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO3F? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (1A′) with a Cs symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO3F?, suggesting that [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions. 相似文献
135.
O. A. Kholdeeva R. I. Maksimovskaya G. M. Maksimov K. I. Zamaraev 《Reaction Kinetics and Catalysis Letters》1998,63(1):95-102
Alkylammonium salts of Ti(IV)-substituted heteropolytungstate, PW11TiO
10
5−
, catalyze the oxidation of methyl phenyl sulfide with hydrogen peroxide. The yield of the corresponding sulfoxide and sulfone
is practically quantitative. A31P NMR study confirms the formation and reactivity of the PW11O39TiO
2
5−
peroxo complex in organic media. 相似文献
136.
ZnS胶体溶液中某些无机盐光化学过程中产生的阴离子自由基的ESR研究 总被引:4,自引:0,他引:4
本文用自旋捕捉与ESR技术相结合的方法研究了ZnS胶体溶液中某些无机盐光化学过程中产生的无机阴离子自由基,并对自由基产生的机理进行了讨论 相似文献
137.
The SIBFA procedure (Sum of Interactions Between Fragments computedAb initio, Ref [1]) is extended to the study of the conformational behavior of representative molecules containing amide nitrogens and carbonyl and carboxylate oxygens. The molecules studied are C- and N-ethylammonium formamide, C- and N-ethanol-formamide, ethylammonium formate and ethanolformate. The cases investigated include interactions of the types which occur between functional groups in proteins or ionophores. The accuracy of the procedure, assessed by comparing the results to those of correspondingab initio SCF computations, is very satisfactory. An application of the procedure to study the conformation of the glycyl and alanyl dipeptides as a function of the backbone torsional angles and is presented. 相似文献
138.
Photocatalytic reactions occurring at semiconductor particles/solution interfaces can be applied to organic syntheses. In this review article, examples of photocatalytic syntheses of cyclic amino acids by suspended semiconductor particles, e.g., titanium(IV) oxide or cadmium(II) sulfide are introduced and interpreted. Different from the photocatalytic decomposition of pollutants under aerobic conditions, selective conversion of organic compounds can be driven by the photocatalytic reactions under deaerated conditions. 相似文献
139.
A New Samarium Nitride Sulfide: Sm4N2S3 The oxidation of samarium with sulfur in the presence of SmCl3 and NaN3 as nitrogen source (molar ratio: 12:9:4:2, evacuated silica vessel, some NaCl as flux, 850°C, 7 d) yields Sm4N2S3 as lath-shaped, dark red single crystals. The by-products (NaCl and NaSm2Cl6) are rinsed with water from the crude product. The crystal structure of Sm4N2S3 (monoclinic, C2/m (no. 12), Z = 2, a = 1 318.04(12), b = 391.57(2), c = 1 031.76(9) pm, β = 130.874(6)°, R = 0.036, Rw = 0.031) contains two crystallographically different Sm3+, both in sixfold coordination of the anions. Besides distorted octahedra [(Sm1)N3S3] and [(Sm2)NS5], tetrahedra [(N3?)(Sm)] connected via two cis-oriented edges to form chains [N(Sm1)3/3(Sm2)1/1]3+ build up the Mayn structural feature. These are arranged in the fashion of a closest packing of rods and held together by two crystallographically different S2? anions which take care for charge neutrality and three-dimensional interconnection. 相似文献
140.
M4X3[Si2O7]-Type Lanthanide Chalcogenide Disilicates (M ? Ce? Er; X ? S, Se) Attempts to produce single crystals of MSe2 (or MSe2?X) by vapour phase transport with iodine or the oxidation of MCl2 (or MClH) with sulfur in the presence of NaCl in sealed evacuated quartz containers often yielded well-grown single crystals with the composition M4X3[Si2O7] (M ? pr, Sm, Gd, X ? Se, and M ? Nd, Er, X ? S) as by-products. The crystal structures (tetragonal, 141/amd (no. 141)), Z = 8, contain two crystallographically independent M3+ Cations that are interconnected by chalcogenide (X2?) and disilicate anions ([Si2O7]6?). (M1)3+ is surrounded by eight (five X2? and three terminal O2? of the disilicate group), (M2)3+ by nine (three X2? and six terminal O2? of the [Si2O7]6? anion) chalcogenide anions. The disilicate anion itself exhibits the eclipsed conformation with non-linear Si? O? Si bridges (angles: 128 – 133°). 相似文献