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51.
Minghui Zhou Marianne Lankelma Dr. Ir. Jarl Ivar van der Vlugt Prof. Dr. Bas de Bruin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11166-11172
The metalloradical activation of o-aryl aldehydes with tosylhydrazide and a cobalt(II) porphyrin catalyst produces cobalt(III)-carbene radical intermediates, providing a new and powerful strategy for the synthesis of medium-sized ring structures. Herein we make use of the intrinsic radical-type reactivity of cobalt(III)-carbene radical intermediates in the [CoII(TPP)]-catalyzed (TPP=tetraphenylporphyrin) synthesis of two types of 8-membered ring compounds; novel dibenzocyclooctenes and unprecedented monobenzocyclooctadienes. The method was successfully applied to afford a variety of 8-membered ring compounds in good yields and with excellent substituent tolerance. Density functional theory (DFT) calculations and experimental results suggest that the reactions proceed via hydrogen atom transfer from the bis-allylic/benzallylic C−H bond to the carbene radical, followed by two divergent processes for ring-closure to the two different types of 8-membered ring products. While the dibenzocyclooctenes are most likely formed by dissociation of o-quinodimethanes (o-QDMs) which undergo a non-catalyzed 8π-cyclization, DFT calculations suggest that ring-closure to the monobenzocyclooctadienes involves a radical-rebound step in the coordination sphere of cobalt. The latter mechanism implies that unprecedented enantioselective ring-closure reactions to chiral monobenzocyclooctadienes should be possible, as was confirmed for reactions mediated by a chiral cobalt-porphyrin catalyst. 相似文献
52.
LIN Hong-Wei 《结构化学》2007,26(7):773-776
A new Schiff base compound, C13H9Br2N3O2·CH3OH, isonicotinic acid [1-(3,5- dibromo-2-hydroxyphenyl)methylidene]hydrazide methanol, has been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The compound comprises a Schiff base moiety isonicotinic acid [1-(3,5-dibromo-2-hydroxyphenyl) methylidene]hydrazide and a methanol molecule. The crystal belongs to the triclinic system, space group P1 with a = 8.464(1), b = 9.511(2), c = 10.901(2) , α = 92.940(2), β = 110.456(2), γ = 96.040(2)o, Z = 2, V = 814.0(2) 3, Dc = 1.759 g/cm3, Mr = 431.09, λ(MoKα) = 0.71073 , μ = 4.994 mm-1, F(000) = 424, R = 0.0440 and wR = 0.1061. A total of 3284 unique reflections were collected, of which 2197 with I > 2σ(I) were observed. The molecule adopts a trans configuration about the C=N double bond. The dihedral angle between the benzene and pyridine rings is 22.0(4)o. The crystal structure is stabilized by intermolecular O-H···N and C-H···O hydrogen bonds, forming layers parallel to the ac plane. The preliminary biological tests show that the compound has potential antibacterial activities. 相似文献
53.
WANG Shou-Wu YANG Yuan LI Bao-Long ZHANG Yong 《结构化学》2007,26(7):763-766
The new cadmium(II) coordination polymer [Cd(bte)2(dca)2]n 1 (bte = 1,2-bis(1,2,4- triazol-1-yl)ethane, dca = dicyanamide) was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.7148(15), b = 8.6142(17), c = 15.204(3) A, β = 92.100(10)o, V = 1140.6(4) A3, Z = 2, Mr = 572.87, Dc = 1.668 g/cm3, F(000) = 572, μ = 1.004 mm-1, the final R = 0.0654 and wR = 0.1429 for 1737 observed reflections (I > 2σ(I)). The cadmium atom is coordinated equatorially by four nitrogen atoms from four bte ligands and axially by two nitrogen atoms from two dca anions to adopt a distorted octahedral geometry. Each bte molecule bridges two cadmium(II) atoms. Two strands of bte molecules are wrapped around each other, and held together by cadmium(II) atoms. 1 Forms a double chain structure containing eighteen-membered Cd2(bte)2 rings. 相似文献
54.
55.
本文研究了具有卷积的中心自反环的性质,定义并引入了中心-自反环,显然,中心-自反环是自反环、中心自反环和-自反环的推广.给出了这类环的一些特征,研究了相关的环扩张,包括平凡扩张,Dorroh扩张和多项式扩张. 相似文献
56.
计算了两共轴均匀带电圆环的相互作用能,并求出它们之间的相互作用力,绘制出电场力的空间分布图,进而讨论了作用力和两圆环半径和中心距离等参量的关系. 相似文献
57.
58.
称环R为广义2-素环,如果R的幂零元集与上诣零根一致.证明了R上的多项式为单位当且仅当它的常数项是R中的单位而其它系数是幂零的.因此,广义2-素环上的多项式环的稳定度大于一. 相似文献
59.
通过利用半单环的结构定理、环的单位群的性质、环的阶及环的单位群的阶的关系等,确定了当n为素数,m=2~(t+1),t为正整数时,群环z_nD_m的代数结构和性质. 相似文献
60.
O.A. Shegai V.I. Mashanov H.-H. Cheng O.P. Pchelyakov 《Physica E: Low-dimensional Systems and Nanostructures》2009,42(1):22-24
At low temperatures a lateral photoconductivity (PC) of Ge/Si (1 0 0) self-organized quantum rings (QRs) structures as a function of interband light intensity has been investigated for different values of lateral voltage and temperature. In contrast to self-organized Ge/Si quantum dots (QDs) structures (grown at the same conditions) where the stepped PC was registered, for QRs structures essential smoothing of PC steps was observed. Such behavior is determined by decreasing of strain potential around QRs in conductive Si matrix due to a transfer of Ge atoms from the center of QDs to its periphery accompanied by Ge/Si intermixing. 相似文献