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61.
In order to study the effects of R group on Fe–Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)3(PPh2R)2 (R=pym:1, fur: 2, py: 3,thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)3(PPh2R)2(HgCl2)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyses were also performed to explain the nature of the Fe–Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atoms there are, the higher is the stabilility of the complex. (2) The Fe–Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, thereisa σ-bond between Fe and Hg atoms. However, in 7 and 8, the Fe–Hg interactions act as σP–Fe→nHg and σC–Fe→nHg delocalization. (3) Through Fe→Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction. 相似文献
62.
改性Y分子筛的酸碱性能及吸附性能的研究 总被引:2,自引:1,他引:2
吡啶、吡咯、苯、甲苯、乙苯作为探针分子,在Li+, Na+, K+, Cs+改性的Y型分子筛上进行吸附,用TPD及IR方法系统地研究了不同碱金属离子改性的Y型分子筛的酸碱性能和吸附性能的变化. 结果表明,按Li、Na、K、Cs的顺序, 随着碱金属离子半径的增大, 其L酸酸强度依次减弱,L碱的强度逐渐增强.由于改性Y型分子筛所含碱金属离子的不同,其对芳烃的吸附的强弱及吸附量的大小亦不同.随着骨架外的阳离子的半径逐渐增大,碱的强度逐渐增强,与芳烃的作用愈强烈,导致TPD脱附峰温增高及芳烃和侧链上的C-H伸缩振动谱带向低波数位移愈多.由于位阻的原因,对含同一种碱金属离子的分子筛来说,随着芳烃侧链C数的增加,芳烃的吸附量逐渐减小. 相似文献
63.
64.
65.
AbstractA simple, efficient, and metal-free methodology for the preparation of 2-mercaptobenzothiazole and derivatives in excellent yields via microwave-assisted pathway is reported. Our condition provides a convenient protocol for the synthesis of a diverse collection of 2-mercaptobenzothiazoles and 6-(4-substituted-1H-1,2,3-triazol-1-yl)-2-mercaptobenzothiazoles with a very simple purification process. This report provides an alternative protocol for fast access to the wide range of compounds for sequence synthesis and biological studies. 相似文献
66.
67.
Jun Zhou Jie Yang Li Qi Xuan Shen Dunru Zhu Yan Xu You Song 《Transition Metal Chemistry》2007,32(6):711-715
A novel dinuclear nickel(II) complex, [Ni2(MOBPT)2Cl2(H2O)2]Cl2 · 7H2O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray
diffraction methods. The crystal structure determination shows that the dinuclear Ni2N8 unit is almost planer in which each NiII ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted
octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex. 相似文献
68.
Peng Yang Xuan Wang Bo Li Yixuan Yang Jinfeng Yue Yanrui Suo Huarong Tong Gang He Xiaojie Lu Gong Chen 《Chemical science》2021,12(16):5804
A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. 相似文献
69.
首先以NaBH4作为强还原剂在CuSO4溶液中快速形成Cu2O晶核, 然后以葡萄糖为温和的还原剂和保护剂, 由晶核生长成Cu2O立方体, 并以其为模板制备中空的球状CuxS纳米笼子. 利用透射电子显微镜(TEM), 扫描电子显微镜(SEM), X射线衍射仪(XRD)和紫外-可见(UV-Vis)分光光度计对产物进行表征. 葡萄糖和铜盐的物质的量的比、加热状况、pH等反应条件影响Cu2O的形貌. CuxS纳米笼子的外壳厚度由参与反应的Cu2O和Na2S的物质的量的比决定. 相似文献
70.
C. Decker H. Le Xuan T. Nguyen Thi Viet 《Journal of polymer science. Part A, Polymer chemistry》1995,33(16):2759-2772
Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 John Wiley & Sons, Inc. 相似文献