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71.
Unsymmetrical Pincer‐Type Ruthenium Complex Containing β‐Protic Pyrazole and N‐Heterocyclic Carbene Arms: Comparison of Brønsted Acidity of NH Groups in Second Coordination Sphere 下载免费PDF全文
Tatsuro Toda Prof. Dr. Shigeki Kuwata Prof. Dr. Takao Ikariya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9539-9542
A reaction of a 2‐(imidazol‐1‐yl)methyl‐6‐(pyrazol‐3‐yl)pyridine with [RuCl2(PPh3)3] resulted in tautomerization of the imidazole unit to afford the unsymmetrical pincer‐type ruthenium complex 2 containing a protic pyrazole and N‐heterocyclic carbene (NHC) arms. Deprotonation of 2 with one equivalent of a base led to the formation of the NHC–pyrazolato complex 3 , indicating that the protic NHC arm is less acidic. When 2 was treated with two equivalents of a base under H2 or in 2‐propanol, the hydrido complex 4 containing protic NHC and pyrazolato groups was obtained through metal–ligand cooperation. 相似文献
72.
Harada T Ikeda S Hashimoto F Sakata T Ikeue K Torimoto T Matsumura M 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17720-17725
A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions. 相似文献
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Ionic liquid crystals based on ionic complexation of tris(2‐aminoethyl)amine (1) with 3,4,5‐tris(7,7,8,8,9,9,10,10,11,11,12,12,12‐tridecafluorododecyloxy)benzoic acid (2) and with 3,4,5‐tris(2‐octyldodecyloxy)benzoic acid (3) were investigated. The ionic complex with the partially fluorinated alkyl chains (1·2) exhibited a morphological transition from a hexagonal columnar mesophase to a Pm3n micellar cubic phase upon increasing the molar ratio of 2 to 1. For the complex with the branched alkyl chains (1·3) a micellar cubic mesophase was exclusively generated at appropriate composite ratios. The generation of the micellar cubic mesophases is attributed to the introduction of the laterally expanded volume of the alkyl chains compared with the corresponding normal dodecyl chains. Their thermal stabilities were most enhanced at a specific molar ratio of 1:5 for 1·2 and 1:4 for 1·3. This result corresponds to the most suitable chain volume for the stable micellar cubic mesophase. 相似文献
77.
Kumar Samir Taneichi Taiga Fukuoka Takao Namura Kyoko Suzuki Motofumi 《Cellulose (London, England)》2021,28(17):10803-10813
Cellulose - Surface-enhanced Raman spectroscopy (SERS)-based biosensors have recently been extensively developed because of their high sensitivity and nondestructive nature. Conventional SERS... 相似文献
78.
Kenji Sakamoto Kiyoaki Usami Kazushi Miki 《Molecular Crystals and Liquid Crystals》2015,611(1):153-159
Photo-alignment efficiency of polyimide containing azobenzene in the backbone structure (Azo-PI) is significantly enhanced by exposing the precursor (polyamic acid: Azo-PAA) film to alkyl-amine vapor prior to photo-alignment. In this study, we have investigated the relationships between the alkyl-amine vapor treatment time, the swelling ratio of Azo-PAA films, and the photo-induced in-plane anisotropy. We found that: the Azo-PAA film swells on exposure to alkyl-amine vapor, and the swelling finally saturates; and the photo-induced in-plane anisotropy is correlated very closely with the swelling ratio. In addition, we pointed out the importance of the process order of alkyl-amine vapor treatment and photo-alignment. 相似文献
79.
Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques 下载免费PDF全文
Dr. Shinobu Takao Dr. Oki Sekizawa Dr. Shin‐ichi Nagamatsu Dr. Takuma Kaneko Dr. Takashi Yamamoto Dr. Gabor Samjeské Dr. Kotaro Higashi Dr. Kensaku Nagasawa Dr. Takuya Tsuji Dr. Motohiro Suzuki Dr. Naomi Kawamura Dr. Masaichiro Mizumaki Prof. Dr. Tomoya Uruga Prof. Dr. Yasuhiro Iwasawa 《Angewandte Chemie (International ed. in English)》2014,53(51):14110-14114
There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation. 相似文献
80.
Takao Tsuneda 《Chemical record (New York, N.Y.)》2020,20(7):618-639
The development of density functional theory (DFT) functionals and physical corrections are reviewed focusing on the physical meanings and the semiempirical parameters from the viewpoint of data science. This review shows that DFT exchange‐correlation functionals have been developed under many strict physical conditions with minimizing the number of the semiempirical parameters, except for some recent functionals. Major physical corrections for exchange‐correlation function‐ als are also shown to have clear physical meanings independent of the functionals, though they inevitably require minimum semiempirical parameters dependent on the functionals combined. We, therefore, interpret that DFT functionals with physical corrections are the most sophisticated target functions that are physically legitimated, even from the viewpoint of data science. 相似文献