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1.
Ab initio calculations have been performed to investigate some of the spectroscopic properties, like geometry, frequency, electron affinity, ionization potential and finally adiabatic bond dissociation energies (BDEs) of lead monohalides, lead dihalides and their ions viz. PbX, PbX±, PbX2, (X ?= ?F, Cl, Br, I) in their ground state at the QCISD(T)//MP2 level of theory using correlation consistent basis sets. For the validation of MP2 optimized geometry and frequency, we further obtained geometry and frequency of all the neutral and ionic systems using QCISD(T) method with the same basis sets. The BDEs of PbX2 molecules are calculated using the BDEs of ions and taking ionization potential and electron affinity of various systems. The calculated values are found in good agreement with the available data. Most of the data for ionic systems are reported first time in literature. 相似文献
2.
A mixed CuI/CuIIcatalyst based on magnetic cysteine functionalized graphene oxide (CuI/II@Cys-MGO) was prepared and used for the azidonation reaction of aryl boronic acids and one-pot synthesis of 1,4-diaryl −1,2,3-triazoles. Aryl azides were obtained in good yields and short reaction times via cross-coupling of aryl boronic acids with sodium azide in the presence of CuII catalytic species in this catalytic system. The azide-alkyne cycloaddition reaction was catalyzed by CuI catalytic species in CuI/II@Cys-MGO nanocomposite. 相似文献
3.
Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators 下载免费PDF全文
Zilong Zhang Pan Hu Xiao Li Hongmei Zhan Yanxiang Cheng 《Journal of polymer science. Part A, Polymer chemistry》2015,53(12):1457-1463
Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt3, PCy3, and P(o‐tol)3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy3 or P(o‐tol)3 exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt3 did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)3 can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463 相似文献
4.
Palladium‐catalyzed decarboxylative coupling of α,β‐unsaturated carboxylic acids with aryl tosylates
We report a general method for selective cross‐coupling of α,β‐unsaturated carboxylic acids with aryl tosylates enabled by versatile Pd(II) complexes. This method features the general cross‐coupling of ubiquitous α,β‐unsaturated carboxylic acids by decarboxylation. The transformation is characterized by its operational simplicity, the use of inexpensive, air‐stable Pd(II) catalysts, scalability and wide substrate scope. The reaction proceeds with high trans selectivity to furnish valuable (E)‐1,2‐diarylethenes. 相似文献
5.
Weimin Shi Jingjie Zhang Fengqian Zhao Wei Wei Fang Liang Yin Zhang Prof. Dr. Shaolin Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14823-14827
In this work, a mild and transition-metal-free approach for the nucleophilic aromatic substitution (SNAr) of unactivated fluoroarenes with primary aliphatic amines to form aromatic amines is reported. This reaction is facilitated by the formation of cationic fluoroarene radical intermediates in the presence of an acridinium-based organic photocatalyst under blue-light irradiation. Various electron-rich and electron-neutral fluoroarenes are competent electrophiles for this transformation. A wide range of primary aliphatic amines, including amino acid esters, dipeptides, and linear and branched amines are suitable nucleophiles. The synthetic utility of this protocol is demonstrated by the late-stage functionalization of several complex drug molecules. 相似文献
6.
Dr. Jindong Ren Dr. Henning Klaasen Melanie C. Witteler Lena Viergutz Prof. Dr. Johannes Neugebauer Dr. Hong-Ying Gao Prof. Dr. Armido Studer Prof. Dr. Harald Fuchs 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16727-16732
The reactivity of aryl triflates in on-surface C−C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π-systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π-systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2-hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations. 相似文献
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A ligand-free, CuI-catalyzed protocol was developed for the one-step preparation of Michael adducts of aromatic thiols in high yields by reacting a mixture of an aryl halide and an electron-deficient alkene with sodium iso-propyl xanthogenate. 相似文献
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