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71.
Walter K. Dean Gary L. Simon Paul M. Treichel Lawrence F. Dahl 《Journal of organometallic chemistry》1973,50(1):193-207
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor. 相似文献
72.
John S. Riley Tomas Baer G. Dean Marbury 《Journal of the American Society for Mass Spectrometry》1991,2(1):69-75
High-resolution mass spectrometry (HRMS), hybrid tandem mass spectrometry (MS/MS) (EBqQ), and photoelectron-photoion coincidence (PEPICO) experiments were conducted to examine a possible ortho-ortho effect resulting in a novel [M - 35]+ fragment ion in 2-alkyl-4, 6-dinitrophenols. For compounds having ethyl or larger alkyl substituents, [M35]+ was observed only when [M - 18]+ ions were present, with the ortho nitro group being involved in the reaction to [M- 35]+. For [M - 18]+ and [M - 35]+, HRMS results were consistent with losses of H2O and H2O + OH, respectively, whereas MS/MS results indicated a sequential reaction due to metastable dissociations. The appearance energy determined by PEPICO for [M - 35]+ was found to be greater than the appearance energy for [M - 18]+, thus supporting a sequential reaction. 69–75). 相似文献
73.
Study on the oligomerization of cyclopentadiene and dicyclopentadiene to tricyclopentadiene through diels-alder reaction 总被引:3,自引:0,他引:3
Zhongqiang Xiong Zhentao Mi Xiangwen Zhang 《Reaction Kinetics and Catalysis Letters》2005,85(1):89-97
Summary The oligomerization of cyclopentadiene (CPD) and its dimer, dicyclopentadiene (DCPD), to tricyclopentadiene (TCPD) through Diels-Alder reaction at temperatures between 120 and 150°C was investigated. The results show that reaction temperature, pressure and solvent influence the product yield; at 150°C up to 50% yield of TCPD was obtained in the absence of solvents. The ratios of isomers A to B in the product can be adjusted by using different solvents. The kinetics indicate that the rate is more sensitive to the concentration of CPD than to that of DCPD. 相似文献
74.
Summary In this paper a database of atomic residual charges has been constructed for all the molecular fragments defined previously in a combinatorial search of the Cambridge Structural Database. The charges generated for the atoms in each fragment are compared with charges calculated for whole molecules containing those fragments. The fragment atomic charges lie within 1 S.D. of the mean for 68%, and within 2 S.D. for 91%, of the atoms whose charges were computed for whole molecules. The actual charges on any atom are strongly influenced by the adjacent connected atoms. There is a large spread of atomic residual charge within the fragments database. 相似文献
75.
合成了3个新型开链冠醚Schiff碱-稀土离子三元配合物RE(H2L)(Mq)(NO3)3,其中RE=Nd3 ,Er3 ,Yb3 ,配体H2L=N,N-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷,Mq为8-羟基喹哪啶.采用元素分析、红外光谱(IR)、紫外-可见吸收光谱(UV-vis)、热重-差热分析(TG-DTG)等手段对配合物的组成结构进行了表征.测定了3种新型结构稀土三元配合物在不同温度(77 K和300 K)时的近红外发光光谱. 相似文献
76.
Siya Ram William Evans Dean S. Wise Leroy B. Townsend John W. Mccall 《Journal of heterocyclic chemistry》1989,26(4):1053-1059
A series of methyl 2-substituted purine 8-carbamates was prepared and evaluated for antifilarial activity. These purines were synthesized as aza congeners of benzimidazole carbamates which have shown significant anthelmintic activity to determine the effect that this modification might have on anthelmintic activity. The compounds were tested against the filarial infection, B. pahangi, in jirds. None of the compounds prepared in this study demonstrated antifilarial activity. 相似文献
77.
Ming Guo Jue Wang Man Xiong Ronghui Wu Xuejuan Yang Jianzhong Zhou Minghui Li Jiajun Li 《大学化学》1986,35(12):237-246
In order to improve university laboratory teaching and practical education under the background of information technology, as well as overcome the difficulty for practical training, develop a virtual simulation experiment platform for rapid pyrolysis of natal materials and high-performance liquid chromatographic (HPLC) detection of its components. The experiment integrates the actual operation process of the plant to produce cleaved products by rapid pyrolysis of biomass with HPLC detection. The virtual experiment is divided into biomass sample pretreatment, rapid biomass pyrolysis, bio-oil extraction, and HPLC determination of complex components, making the biomass cleavage workshop "real" through simulation. This virtual simulation experiment fully integrates the utilization of biomass resources and basic chemistry courses (such as organic chemistry, instrumental analysis, chemical engineering principles, etc.), which are widely involved in agricultural and forestry majors with advantageous characteristics value. 相似文献
78.
Addition of a benzyl substituent to the macrocyclic ring of DOTA has a substantial impact on the conformational ring flipping motion of the macrocycle in the resulting LnDOTA complexes. The p-NO2-benzyl substituent in the Ln(p-NO2-Bn-DOTA)- complexes lies in an equatorial position and effectively "locks" the conformation of the ring into the deltadeltadeltadelta configuration. The presence of the p-NO2-benzyl group also increases the population of the square antiprismatic (SAP) coordination isomer for all Ln(p-NO2-Bn-DOTA)- complexes relative to that seen for the respective LnDOTA- complexes. Despite this increase in SAP isomer population, the rate of water exchange in these complexes remains comparatively fast. The kinetic and thermodynamic stabilities of the Ln(p-NO2-Bn-DOTA)- complexes are also slightly lower than the corresponding LnDOTA- complexes but appear to be sufficiently high for in vivo use. 相似文献
79.
This study presents a novel miniaturized Hadamard transform fluorescence imaging microscope, by combining a conventional fluorescence microscope with Hadamard transform multiplexing encoding using a one-dimensional movable mask to realize spatial resolution and a linear CCD for multichannel detection. The microscope can provide high-resolution automatically-generated 0–255 gray level HT images for morphological analysis and visualization of a single cell, and normalized HT images for cellular quantitative measurements. The microscopes imaging capability was applied to measure the DNA content in human lymphocyte, chicken erythrocyte and eel erythrocyte, and a comparative study was performed. The results show that the calibrated DNA content in a chicken erythrocyte is 2.32 pg when human lymphocyte is used as the standard, and eel erythrocyte may be a potentially reliable and novel standard for determining DNA contents in other species because it has a stable DNA value of 2.06 pg, with a CV of 4.3% when 20 eel erythrocytes are measured. The results also demonstrate that the HT imaging microscope should be valuable in the fields of medicine and cell biology. 相似文献
80.
A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of masstransfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performancefor hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of thetraditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersedRh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation ofhigher olefins such as 1-dodecene. 相似文献