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1.
H. Schumann 《Angewandte Chemie (International ed. in English)》1969,8(12):937-950
The preparation, properties, and reactions of the compounds named in the title are described, with particular reference to the possible participation of (p→d)π components in the bonding between the group IVB and the group VB elements. 相似文献
2.
Dr. Wenlong Yang Dr. Jorge H. S. K. Monteiro Prof. Ana de Bettencourt‐Dias Prof. Vincent J. Catalano Prof. Wesley A. Chalifoux 《Angewandte Chemie (International ed. in English)》2016,55(35):10427-10430
The design of a relatively simple and efficient method to extend the π‐conjugation of readily available aromatics in one‐dimension is of significant value. In this paper, pyrenes, peropyrenes, and teropyrenes were synthesized through a double or quadruple benzannulation reaction of alkynes promoted by Brønsted acid. This novel method does not involve cyclodehydrogenation (oxidative aryl–aryl coupling) to arrive at the newly incorporated large arene moieties. All of the target compounds were synthesized in moderate to good yields and were fully characterized with the structures unambiguously confirmed by X‐ray crystallography. As expected, photophysical characterization clearly shows increasing red‐shifts as a function of extended conjugation within the fused ring systems. 相似文献
3.
C. Peter Sebastian Constanze Fehse J. Paul Attfield Sudhindra Rayaprol Rainer Pöttgen 《Journal of solid state chemistry》2006,179(8):2376-2385
The rare earth-silver-stannides YAgSn, TmAgSn, and LuAgSn were synthesized from the elements by arc-melting and subsequent annealing. The three stannides were investigated by X-ray powder and single-crystal diffraction: NdPtSb type, P63mc, Z=2, a=468.3(1), pm, wR2=0.0343, 353 F2 values, 12 variables for YAgSn, and ZrNiAl type, P6¯2 m, a=726.4(2), , wR2=0.0399, 659 F2 values, 15 variables for TmAgSn, and a=723.8(2), , wR2=0.0674, 364 F2 values, 15 variables for LuAgSn. Besides conventional laboratory X-ray data with monochromatized Mo radiation, the structures were also refined on the basis of synchrotron data with , in order to clarify the silver-tin ordering more precisely. YAgSn has puckered, two-dimensional [AgSn] networks with Ag-Sn distances of 278 pm, while the [AgSn] networks of TmAgSn and LuAgSn are three-dimensional with Ag-Sn distances of 279 and 284 pm for LuAgSn. Susceptibility measurements indicate Pauli paramagnetism for YAgSn and LuAgSn. TmAgSn is a Curie-Weiss paramagnet with an experimental magnetic moment of 7.2 μB/Tm. No magnetic ordering is evident down to 2 K. The local environments of the tin sites in these compounds were characterized by 119Sn Mössbauer spectroscopy and solid-state NMR (in YAgSn and LuAgSn), confirming the tin site multiplicities proposed from the structure solutions and the absence of Sn/Ag site disordering. Mössbauer quadrupolar splittings were found in good agreement with calculated electric field gradients predicted quantum chemically by the WIEN2k code. Furthermore, an excellent correlation was found between experimental 119Sn nuclear magnetic shielding anisotropies (determined via MAS-NMR) and calculated electric field gradients. Electronic structure calculations predict metallic properties with strong Ag-Sn bonds and also significant Ag-Ag bonding in LuAgSn. 相似文献
4.
Piers WE Bourke SC Conroy KD 《Angewandte Chemie (International ed. in English)》2005,44(32):5016-5036
Boron cations are elusive and highly electrophilic species that play a key role in the chemistry of boron. Despite early interest in the chemistry of boron cations, until recently they have largely remained chemical curiosities. However, hints at harnessing their potential as potent electrophiles have begun to appear and developments in weakly coordinating anion technology suggest that this is an area of research that is ripe for exploration. It has been nearly 20 years since the last major review on boron cations; herein we summarize the progress in the area since that time. 相似文献
5.
Wenlong Yang Jorge H. S. K. Monteiro Ana deBettencourt‐Dias Vincent J. Catalano Wesley A. Chalifoux 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(35):10583-10586
The design of a relatively simple and efficient method to extend the π‐conjugation of readily available aromatics in one‐dimension is of significant value. In this paper, pyrenes, peropyrenes, and teropyrenes were synthesized through a double or quadruple benzannulation reaction of alkynes promoted by Brønsted acid. This novel method does not involve cyclodehydrogenation (oxidative aryl–aryl coupling) to arrive at the newly incorporated large arene moieties. All of the target compounds were synthesized in moderate to good yields and were fully characterized with the structures unambiguously confirmed by X‐ray crystallography. As expected, photophysical characterization clearly shows increasing red‐shifts as a function of extended conjugation within the fused ring systems. 相似文献
6.
A systematic quantum chemical investigation of mono-, di-, and triaminoborane, -alane, -gallane, and -indane is carried out to determine quantitatively the effects of pi bonding and negative hyperconjugation on structures, energetics, and rotational barriers in these systems. Pi bonding plays a significant role in the aminoborane compounds, but becomes rapidly less significant in the aminoalanes, -gallanes, and -indanes. For each main-group metal X investigated, X-N rotational barriers are found to be essentially equal depending only on the number of remaining in-plane amino groups. The contribution of negative hyperconjugation to reducing rotational barriers, as assessed from natural bond orbital (NBO) delocalization energies, is independent of the pyramidalization of the out-of-plane amino group, and is also dependent only on the number of rotated groups. Optimized tris[bis(trimethylsilyl)amino]-substituted structures of boron, aluminum, gallium, and indium are found to compare quite well with available experimental structural data, and exhibit X-N torsion angles that are independent of the central metal atom. 相似文献
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A new protocol for the Ullmann-type arylation process of different aromatic heterocycles without any transition-metal catalyst, implying the use of a combination of an excess of potassium hydroxide and dimethyl sulfoxide, is described. The reaction can be performed between a broad range of starting nucleophiles including phenol, alcohols, amines, nitrogen-containing five-membered systems such as pyrazoles, imidazoles, and indoles, and amides with haloarenes, iodide and bromide derivatives giving the best results, the possible pathway involving the in situ generation of the corresponding benzyne intermediate. When the reaction was performed with 2-iodoaniline and either carboxamides or isothiocyanato derivatives, the corresponding benzoazole derivatives were obtained. 相似文献
9.
布兰顿首先将“规范”当作人类活动的核心特征,并以实用主义的方式回答了规范的性质问题;然后再由规范引出推论作为语言意义的根据,并澄清了实质推论的基础地位;接着又进一步,细致解析了推论的实际运作机制,将推论落实于社会交往的过程之中,认为社会交往本质上是不同成员之间的道义计分;最后,在推论主义框架下解释了真、表象语汇的必要性,并对语言与世界的关系做出了推论主义的说明。他的哲学体系由规范、推论、交往、世界四个维度组成。它们层层递进,形成了一个具有严密内在结构的有机整体。原本分散甚至对立的论题,在此得到整合。 相似文献
10.
Rolf W. Saalfrank Norbert Löw Bernhard Demleitner Dietmar Stalke Markus Teichert 《Chemistry (Weinheim an der Bergstrasse, Germany)》1998,4(7):1305-1311
Efficacious metal control of self-assembly of dialkylketipinate dianions leads to completely different supramolecular assemblies. The structures of grid 1 , double-decker 2 , triple-decker 3 , and metalla-spherand 4 were characterized by X-ray crystallographic analyses or by NMR spectroscopy. 相似文献
11.
V. V. Gavrilenko L. A. Chekulaeva I. A. Savitskaya I. A. Garbuzova 《Russian Chemical Bulletin》1992,41(11):1957-1959
A convenient and practical method is proposed for the synthesis of lanthanide and yttrium alkoxides. The method involves dissolving the metals or their hydrides in a solution of dry HCl in the corresponding alcohol, with subsequent dehalogenation of the LnCl3 solution by an equivalent amount of alkali metal (Na, Li), The rareearth alkoxides are easily converted into acetylacetonates Ln(acac)3 by the action of acetylacetone.A. N. Nesmeyanov Institute of Elementoorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2490–2493, November, 1992. 相似文献
12.
Shlomo Margel Erika Wiesel 《Journal of polymer science. Part A, Polymer chemistry》1984,22(1):145-158
Monodisperse polyacrolien (PA) microspheres were obtained by a single step process via two mechanisms: (a) aqueous polymerization of acrolein under alkaline conditions and (b) aqueous radical polymerization of acrolein by irradiation with a cobalt source. The diameter of the former microspheres can be varied from 0.04 up to 8 μm. The monodispersity of the system is also discussed. The diameter of the latter microspheres can be varied up to 0.2 μm. Hybrido PA microspheres were formed by grafting PA microspheres of average diameter of 0.1 μm obtained by irradiation onto the surface of PA microspheres produced by the alkaline mechanism. The aldehyde content of the microspheres prepared by irradiation is much higher than those of the microspheres formed under alkaline conditions. The aldehyde groups were used for the covalent binding of ligands containing primary amino groups, such as proteins and drugs, in a single step under physiological pH. 相似文献
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14.
Hidefumi Nakatsuji 《Tetrahedron》2007,63(48):12071-12080
We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid. 相似文献
15.
铬,硒,镉,锰与心脑血管疾病 总被引:1,自引:0,他引:1
通过对50例心脑血管疾病病人及50例健康对照组血中微量元素铬、硒、镉、锰的检测分析证实,心脑血管疾病病人血清Cr、Se含量下降,Cd含量未见明显升高,并进一步探讨了这些微量元素与心脑血管疾病的发生发展的关系及其临床意义。 相似文献
16.
Various low-dimensional nanostructures, such as nanowires, nanotubes, nanosheets, and fullerene-like nanoparticles have been selectively synthesized from rare-earth compounds (hydroxides, fluorides) based on a facile hydrothermal method. The subsequent dehydration, sulfidation, and fluoridation processes lead to the formation of rare-earth oxide, oxysulfide, and oxyhalide nanostructures, which can be functionalized further by doping with other rare-earth ions or by coating with metal nanoparticles. Owing to the interesting combination of novel nanostructures and functional compounds, these nanostructures can be expected to bring new opportunities in the vast research areas of and application in biology, catalysts, and optoelectronic devices. 相似文献
17.
High quality SCF-MO calculations are reported for the title molecules, including geometry optimization. One-electron properties are presented and discussed, and relative stabilities of (HOS, HSO) and (FOS, FSO) compared. Little experimental geometric data are available at present, but the calculated and experimental geometries of HO2 agree well. 相似文献
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19.
Combined analytical procedures consisting of wet digestion step followed by instrumental determination – differential pulse
cathodic stripping voltammetry (DPCSV) or electrothermal atomic absorption spectrometry (ETAAS) – as well as a direct analysis
method – slurry sampling ETAAS – for the determination of Cd, Co, Cr, Cu, Fe, Ni and Pb in milk, cheese and chocolate are
described and compared. Wet digestion using a mixture of HNO3-HClO4-H2O2 is proposed for complete matrix decomposition prior to trace analyte determinati on by DPCSV or ETAAS. A mixture of HNO3-H2O2 is used for slurry preparation. Optimal instrumental parameters for trace analyte measurements are presented.
The reliability of the procedures has been verified by analyzing standard reference materials. Results obtained are in good
agreement with the certified values and the relative standard deviations (for these results) are in the range 5–10% for wet
digestion DPCSV or ETAAS and 3–9% for slurry sampling ETAAS in the range of 2 μgċg−1 (Cd) to 12 μgċg−1 (Fe).
Received August 24, 1999. Revision January 20, 2000. 相似文献
20.
E. B. Rakhimova I. V. Ozden A. G. Ibragimov 《Russian Journal of Organic Chemistry》2018,54(7):961-986
The review systemizes and generalizes published data on the catalytic syntheses of six-, seven-, and eight-membered S,N-heterocycles and O,N-, S,N-, and O,S,N-macroheterocycles. 相似文献