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11.
Yoshiyuki Tanaka Makoto Arakawa Yohei Yamaguchi Chieko Hori Masahiro Ueno Takeyuki Tanaka Tatsushi Imahori Yoshinori Kondo 《化学:亚洲杂志》2006,1(4):581-585
A metal‐free acetylide was observed by using NMR spectroscopy. Metal‐free acetylides are closely related to reactive intermediates (carbanions) in solution; therefore, they have been regarded as unobservable species. However, we generated this highly reactive and unstable species through the deprotonation of phenylacetylene by using the strong nonmetallic phosphazene base tBu‐P4. In the presence of tBu‐P4, the J coupling between the ethynyl carbon and hydrogen nuclei (1JC,H) of phenylacetylene disappeared; this indicates the deprotonation of the alkyne terminal. Furthermore, a large low‐field shift (approximately 90 ppm) of the alkyne carbon resonance was observed. We concluded that we have observed a metal‐free carbanion with a formal charge on an sp‐hybridized carbon atom for the first time. 相似文献
12.
Chen A Kamata K Nakagawa M Iyoda T Haiqiao Wang H Li X 《The journal of physical chemistry. B》2005,109(39):18283-18288
We have recently demonstrated a one-step process to fabricate silver-polypyrrole (PPy) coaxial nanocables (Chen, A.; Wang, H.; Li, X. Chem. Commun. 2005, 14, 1863). The formation process of silver-PPy coaxial nanocables is discussed in this article. It was found from the results of TEM and SEM images that large numbers of silver atoms were formed when AgNO3 was added to a pyrrole solution. Then silver atoms transform to silver-PPy nanosheets with regular morphology, which will connect together to be more stable. Silver-PPy nanocables will be able to grow at the expense of the silver-PPy nanosheets. Poly(vinylpyrrolidone) (PVP) plays crucial roles in this process: as a capping agent to form silver nanowires, and as a dispersant of pyrrole monomers, which can influence the site at which pyrrole monomer exists. On the basis of experimental analysis, the possible mechanism was proposed. Because of the effect of PVP, silver ions and pyrrole monomers are apt to be adsorbed at the [111] and [100] facets of silver nanosheets, respectively. Obvious polymerization will take place on the boundary of the [111] and [100] facets. The PPy layer stays stable on the [100] facets. Meanwhile, newly formed silver atoms and silver nanosheets will further ripen and grow on the [111] facets. In a word, the morphology of final products and the formation process are determined by the reaction site between AgNO3 and the pyrrole monomer, which is influenced by PVP. 相似文献
13.
Yoshio Imai Hiroshi Kamata Masa-Aki Kakimoto 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1259-1265
Aromatic polyphosphonates of high molecular weights were prepared from phenylphosphonic dichloride and bisphenols having rigid ring structures by the two-phase polycondensation in organic solvent–aqueous alkaline solution system with phase-transfer catalyst at 0°C or below. The effects of reaction solvent and catalyst on the inherent viscosities of the polymers formed are studied. The glass transition temperatures of the polyphosphonates with biphenyl, phenylindane, and diphenylfluorene units are 120, 124, and 188°C, respectively. These polymers are self-extinguishing and are readily soluble in solvents such as N,N-dimethylacetamide, pyridine, tetrahydrofuran, and chloroform. They began to lose weight above 300°C in air. Copolyphosphonates from combinations of bisphenols and phenylphosphonic dichloride are also prepared and characterized. 相似文献
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The paper concerns characterization of BMO in terms of Banach function spaces. In particular, we are interested in characterizing BMO by using the variable Lebesgue norm. 相似文献
17.
Arylpyrrolyldiketone boron complexes as anion‐responsive π‐electronic molecules were synthesized by Claisen condensations of acetylpyrrole and corresponding aryl esters. The synthesized π‐electronic molecules exhibited anion‐binding behavior with various binding modes including pyrrole‐inverted and non‐inverted [1+1]‐type anion complexes as well as [2+1]‐type complexes owing to the presence of only a single pyrrole ring. Furthermore, solid‐state ion‐pairing assemblies, comprising receptor–anion complexes and countercations, were constructed based on fairly planar [2+1]‐type complexes. 相似文献
18.
Dr. Yohei Ogiwara Yurika Iino Prof. Dr. Norio Sakai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6513-6516
A method for the palladium/copper-catalyzed direct acylation of azoles with acyl fluorides is described. This study reports the first examples of acyl fluorides being used as acylation reagents in transition-metal-catalyzed aromatic C−H bond functionalization reactions. Depending on the reaction temperature, decarbonylative coupling may also occur. Mechanistic studies suggest that the cleavage of the aromatic C−H bond, promoted by a copper-phosphine species, is not the rate-limiting step of this acylation. 相似文献
19.
Synthesis,Properties, and Redox Behavior of 1,1,4,4‐Tetracyano‐2‐ferrocenyl‐1,3‐butadienes Connected by Aryl,Biaryl, and Teraryl Spacers
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Dr. Taku Shoji Akifumi Maruyama Chisa Yaku Natsumi Kamata Prof. Dr. Shunji Ito Dr. Tetsuo Okujima Prof. Dr. Kozo Toyota 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):402-409
Aryl‐substituted 1,1,4,4‐tetracyano‐1,3‐butadienes (FcTCBDs) and bis(1,1,4,4‐tetracyanobutadiene)s (bis‐FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro‐electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis‐FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi‐electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 相似文献
20.
Kazuhisa Sato Shunya Tashiro Shuhei Matsunaga Yohei Yamaguchi Takanori Kiguchi Toyohiko J. Konno 《哲学杂志》2018,98(21):1945-1960
We have studied three-dimensional (3D) structures and growth processes of 14H-type long-period stacking order (LPSO) formed in Mg97Zn1Gd2 cast alloys by single tilt-axis electron tomography (ET) using high-angle annular dark-field scanning transmission electron microscopy. Evolution of the solute-enriched stacking faults (SFs) and the 14H LPSO by ageing were visualised in 3D with a high spatial resolution in multi-scale fields of views from a few nanometres to ~10 μm. Lateral growth of the solute-enriched SFs and the LPSO in the (0?0?0?1)Mg plane is notable compared to the out-of-plane growth in the [0?0?0?1]Mg direction. The 14H LPSO grows at the cost of decomposition of the (Mg, Zn)3Gd-type precipitates, and accompany a change of in-plane edge angles from 30 to 60°. We have updated the Time–Temperature–Transformation diagram for precipitation in Mg97Zn1Gd2 alloys: starting temperatures of both solute-enriched SFs and LPSO formation shifted to a shorter time side than those in the previous diagram. 相似文献