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51.
We have developed asymmetric Mukaiyama aldol reactions of silicon enolates with aldehydes catalyzed by chiral FeII and BiIII complexes. Although previous reactions often required relatively harsh conditions, such as strictly anhydrous conditions, very low temperatures (?78 °C), etc., the reactions reported herein proceeded in the presence of water at 0 °C. To find appropriate chiral water‐compatible Lewis acids for the Mukaiyama aldol reaction, many Lewis acids were screened in combination with chiral bipyridine L1 , which had previously been found to be a suitable chiral ligand in aqueous media. Three types of chiral catalysts that consisted of a FeII or BiIII metal salt, a chiral ligand ( L1 ), and an additive have been discovered and a wide variety of substrates (silicon enolates and aldehydes) reacted to afford the desired aldol products in high yields with high diastereo‐ and enantioselectivities through an appropriate selection of one of the three catalytic systems. Mechanistic studies elucidated the coordination environments around the FeII and BiIII centers and the effect of additives on the chiral catalysis. Notably, both Brønsted acids and bases worked as efficient additives in the FeII‐catalyzed reactions. The assumed catalytic cycle and transition states indicated important roles of water in these efficient asymmetric Mukaiyama aldol reactions in aqueous media with the broadly applicable and versatile catalytic systems. 相似文献
52.
53.
Dr. Mark Feyand Milan Köppen Prof. Dr. Gernot Friedrichs Prof. Dr. Norbert Stock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12537-12546
A systematic investigation of the systems Bi3+/carboxylic acid/HNO3 for the tri‐ and tetracarboxylic acids pyromellitic acid (H4Pyr), trimellitic acid (H3Tri) and trimesic acid (H3BTC) acid led to the discovery of five new bismuth carboxylates. Structural characterisation allowed the influence of the linker geometry and the Bi3+:linker molar ratio in the starting solution on the crystal structure to be determined. The crystallisation of three selected compounds was investigated by in situ energy‐dispersive X‐ray diffraction. Three new crystalline intermediates were observed within minutes, and two of them could be isolated by quenching of the reaction mixture. Their crystal structures were determined from laboratory and synchrotron X‐ray powder diffraction data and allowed a possible reaction pathway to be established. In depth characterisation of the luminescence properties of the three bismuth pyromellate compounds was carried out. Fluorescence and phosphorescence could be assigned to (mainly) ligand‐ and metal‐based transitions. The polymorphs of Bi(HPyr) exhibit different luminescence properties, although their structures are very similar. Surprisingly, doping of the three host structures with Eu3+ and Tb3+ ions was only successful for one of the polymorphs. 相似文献
54.
Dr. Madleen Busse Iman Trinh Prof. Peter C. Junk Assoc. Prof. Richard L. Ferrero Prof. Philip C. Andrews 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(17):5264-5275
The synthesis and characterisation of nine new tris‐substituted bismuth(III) aminoarenesulfonates of the general formula [Bi(O3S‐RN)3] (RN=o‐aminophenyl 1 , m‐aminophenyl 2 , 6‐amino‐3‐methoxyphenyl 3 , p‐aminophenyl 4 , 2‐pyridyl 5 , o‐aminonaphthyl 6 , 5‐aminonaphthyl 7 , 4‐amino‐3‐hydroxynaphthyl 8 and 5‐isoquinolinyl 9 ) is described. Two synthetic strategies, using Ag2O and [Bi(OtBu)3], were explored and compared. The possibility to access heteroleptic bismuth(III) complexes with the new silver(I) metathesis reaction is demonstrated with the synthesis of the heteroleptic bismuth(III) aminoarenesulfonate complexes [PhBi(O3S‐P2)2(dmso)] 10 , [Ph2Bi(O3S‐P2)]∞ 11 and [PhBi(O3S‐P2)2]∞ 12 , of which the solid state structures 10 and 12 are presented (2P‐SO3?=2‐pyridinesulfonate). These complexes offer remarkable in‐vitro activity against three standard laboratory strains of Helicobacter pylori (H. pylori) as demonstrated by their exceptionally low minimum inhibitory concentration (MIC) values of 0.049 μg mL?1 for the strains 251 and B128, which places most MIC values in the nano‐molar region. These results demonstrate the importance of the amino functionality in addition to the sulfonate group on the bactericidal properties against H. pylori. 相似文献
55.
Xiyan Li Wei Gao Prof. Hongjie Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2889-2894
Self‐assembled Bi2Te3 one‐dimensional nanorod bundles have been fabricated by a low‐cost and facile solvothermal method with ethylene diamine tetraacetic acid as an additive. The phase structures and morphologies of the samples were characterized by X‐ray diffraction, scanning electron microscopy, Fourier‐transform infrared spectrometry, and transmission electron microscope measurements. The growth mechanisms have been proposed based on the experimental results. The full thermoelectric properties of the nanorod bundles have been characterized and show a large improvement in the thermal conductivity attributed to phonon scattering of the nanostructures and then enhance the thermoelectric figure of merit. This work is promising for the realization of new types of highly efficient thermoelectric semiconductors by this method. 相似文献
56.
以硼酸和碳酸盐为原料,用高温固相法制备了可被(近)紫外光(369、254 nm)有效激发的Tb3+单掺杂LiBa1-xBO3:xTb3+(物质的量分数x=0.02、0.03、0.04、0.05、0.06、0.07)及Bi3+和Tb3+共掺杂LiBa0.95-yBO3:0.05Tb3+,yBi3+(物质的量分数y=0.02、0.03、0.04、0.05、0.06、0.07)的2个系列荧光粉,产物的结构和形貌分别用粉末X射线衍射(PXRD)和扫描电子显微镜进行表征。PXRD测定结果表明2个系列的产物均为纯相LiBaBO3。通过对第一系列产物荧光光谱的测定,筛选出发光强度最好的产物,据此确定铽离子的最佳掺杂量;在此基础上制备出铋离子掺杂量不同的第二系列荧光粉。荧光光谱测定的实验结果表明,Tb3+/Bi3+共掺杂的荧光粉的发光强度好于Tb3+单掺杂的荧光粉,这说明Bi3+对Tb3+有敏化作用;而且随着Bi3+掺杂量的增加,产物的荧光强度表现出先增加后减小的趋势,当Bi3+的掺杂量y=0.03时,产物的荧光强度达到最大。Bi3+和Tb3+之间存在偶极-四极相互作用而进行能量传递。系列荧光粉的CIE坐标显示其发光颜色在一定程度上呈现出由绿色光到白光的渐变趋势。 相似文献
57.
58.
Strong Stokes and Upconversion Luminescence from Ultrasmall Ln3+‐Doped BiF3 (Ln=Eu3+, Yb3+/Er3+) Nanoparticles Confined in a Polymer Matrix
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Heavy metal fluorides like BiF3 as a host for lanthanide ions are of interest as bismuth is the only heavy metal that is nontoxic. In this work, we report the synthesis of highly water‐dispersible ultrasmall BiF3 nanoparticles about 6 nm in size within a poly(vinyl pyrrolidone) matrix by a hydrothermal method. Microscopy analysis reveals that the nanoparticles are well separated and confined within the polymer network. These nanoparticles were found to be excellent hosts for lanthanide (Ln3+) ions. Through suitable Ln3+ doping, BiF3 exhibits strong emissions in the visible region upon both UV and near infrared (NIR) excitations. The non‐toxicity of both bismuth and PVP can be advantageous for the potential use of BiF3 nanoparticles in drug delivery and bioimaging. 相似文献
59.
Tobias Dunaj Prof. Dr. Carsten von Hänisch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202202932
In this work, we report the preparation of multiple interpnictogen chain compounds with three consecutive pnictogen atoms and terminal Ar2Bi fragments (Ar=Ph, Mes). Symmetrical compounds of the form Ar2Bi−E(tBu)−Bi2Ar ( 1 : Ar=Ph, E=P; 2 : Ar=Ph, Mes, E=As) as well as ternary interpnictogen compounds of the form Ar2Bi−E1(tBu)−E2tBu2 (Ar=Ph, Mes; 4 : E1=P, E2=As; 5 : E1=P, E2=Sb; 6 : E1=As, E2=P) were prepared. The decomposition in solution at room temperature and under the influence of light was studied for compounds 1 – 6 . The reactivity of 1Ph and 2Ph with the small N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (Me2IMe) was also studied. In the case of 1Ph , the formation and consecutive decomposition of Me2IMe=PtBu ( 8 ) was observed in solution. Hence, it was shown that 1Ph can react as a “masked phosphinidene”. In the case of 2Ph , no reaction with Me2IMe was observed. All isolated compounds were analysed by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction. 相似文献
60.
Bi2S3 was dissolved in the presence of NaCl in the ionic liquid [BMIm]Cl ⋅ 4AlCl3 (BMIm=1-n-butyl-3-methylimidazolium) through annealing the mixture at 180 °C. Upon cooling to room temperature, orange, air-sensitive crystals of Na(Bi7S8)[S(AlCl3)3]2[AlCl4]2 ( 1 ) precipitated. X-ray diffraction on single-crystals of 1 revealed a triclinic crystal structure that contains (Bi7S8)5+ spiro-dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and sodium cations. 相似文献