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Ye Ji Kim Sun Min Kim Eun Jin Cho Hideo Hosono Jung Woon Yang Sung Wng Kim 《Chemical science》2015,6(6):3577-3581
A simple and highly efficient transfer hydrogenation of alkynes and alkenes by using a two-dimensional electride, dicalcium nitride ([Ca2N]+·e–), as an electron transfer agent is disclosed. Excellent yields in the transformation are attributed to the remarkable electron transfer efficiency in the electride-mediated reactions. It is clarified that an effective discharge of electrons from the [Ca2N]+·e– electride in alcoholic solvents is achieved by the decomposition of the electride via alcoholysis and the generation of ammonia and Ca(OiPr)2. We found that the choice of solvent was crucial for enhancing the electron transfer efficiency, and a maximum efficiency of 80% was achieved by using a DMF mixed isopropanol co-solvent system. This is the highest value reported to date among single electron transfer agents in the reduction of C–C multiple bonds. The observed reactivity and efficiency establish that electrides with a high density of anionic electrons can readily participate in the reduction of organic functional groups. 相似文献
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Jiazhen Wu Jiang Li Yutong Gong Masaaki Kitano Takeshi Inoshita Hideo Hosono 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):835-839
Electrides loaded with transition‐metal (TM) nanoparticles have recently attracted attention as emerging materials for catalytic NH3 synthesis. However, they suffer from disadvantages associated with the growth and aggregation of nanoparticles. TM‐containing intermetallic electrides appear to be promising catalysts with the advantages of both electrides and transition metals in a single phase. LaRuSi is reported here to be an intermetallic electride with superior activity for NH3 synthesis, and direct evidence is provided supporting its electride‐character‐induced catalytic performance. The discussion is made mainly based on the contrasting synthesis rates over the isostructural compounds LaRuSi, CaRuSi, and LaRu2Si2, and the N2 isotope‐exchange reactions over these compounds. Lattice hydride ions, which can reversibly exchange with anionic electrons, are shown to be indispensable in the promotion of NHx formation. The mechanism derived from the present findings provides new guidelines for NH3 synthesis. 相似文献
5.
Tae Hee Kim Hyun Mo Lee Hee Soo Park Sung Dong Kim Su Jin Kwon Atsushi Tahara Hideo Nagashima Bun Yeoul Lee 《应用有机金属化学》2019,33(4)
The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C6F5)4]?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt2)2]+[B(C6F5)4]? and one equivalent CrCl3(THF)3 to (acac)AlEt2 and subsequent treatment with a PNP ligand [CH3(CH2)16]2C(H)N(PPh2)2 ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl3(THF)]2+[B(C6F5)4]?2, which exhibited high activity when combined with iBu3Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)3, iPrN(PPh2)2, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe3, –Si(nBu)3, or –SiMe2(CH2)7CH3 at the para‐position of phenyl groups in 1 (i.e., by using [CH3(CH2)16]2C(H)N[P(C6H4‐p‐SiR3)2]2 instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE. 相似文献
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Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene,Methyl Methacrylate,and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling 下载免费PDF全文
So‐ichiro Nakanishi Dr. Mitsunobu Kawamura Hidetomo Kai Prof. Dr. Ren‐Hua Jin Dr. Yusuke Sunada Prof. Dr. Hideo Nagashima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5802-5814
Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R3TACN) ligands. Two types of structures were confirmed by crystallography: “[(R3TACN)FeX2]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R3TACN)Fe(μ‐X)3Fe(R3TACN)]+ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R3TACN)FeX2]n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)3TACN}FeBr2] ( 4 b ) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined. 相似文献
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Swinhoeisterol A is a novel steroid with unusual 6/6/5/7 tetracyclic skeleton. The model compound with BCD rings is constructed by Friedel–Crafts acylation and an oxidative dearomatization as key steps. 相似文献
9.
Carolina de Melo Conti Hideo Suzuki Aguinaldo Silva Garcez Selly Sayuri Suzuki 《Photochemistry and photobiology》2019,95(5):1249-1257
The aim of this study was to evaluate the effects of photobiomodulation on the repair of induced root resorption (RR) after orthodontic tooth movement. Twenty male rats were used in this study. Forty right and left upper first molars were evaluated and divided into four groups (n = 10): negative control group (NC), no tooth movement or irradiation; positive control group (PC), induced tooth movement and root resorption; conventional treatment group (CT), force was removed after 7 days; and photobiomodulation group (PBM) after force removal molars were irradiated every 48 h for 7 days using GaAlAs diode laser (810 nm). Energy per point was 1.5 J (100 mW, 15 s, 75 J cm?2). NC and PC were euthanized on day 7; CT and PBM on day 14. Histomorphometric and immunohistochemsitry analyses showed increase in area of root resorption in all groups (P < 0.05) compared to NC. RR lacunae were larger in CT compared to PC and PBM at the compression side of the distal root. OPG was higher in PBM group (P < 0.05). PBM group showed low expression of RANKL compared to PC and CT on the tension side. PBM can potentially affect RR progression by increasing OPG expression in the compression area and decreasing number of clastic cells in the root surface. 相似文献
10.
Hiroshi Mizoguchi SangWon Park Haruhiro Hiraka Kazutaka Ikeda Toshiya Otomo Hideo Hosono 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(10):2975-2978
Using a high pressure technique and the strong donating nature of H−, a new series of tetragonal La2Fe2Se2O3‐type layered mixed‐anion arsenides, Ln2M2As2Hx, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x≈3). In these compounds, an unusual M2H square net, which has anti CuO2 square net structures accompanying two As3− ions, is sandwiched by (LaH)2 fluorite layers. Notably, strong metal–metal bonding with a distance of 2.80 Å was confirmed in La2Ti2As2H2.3, which has metallic properties. In fact, these compounds are situated near the boundary between salt‐like ionic hydrides and transition‐metal hydrides with metallic characters. 相似文献