42254-91-1Relevant articles and documents
Invisible Silver Guests Boost Order in a Framework That Cyclizes and Deposits Ag3Sb Nanodots
Ahn, Dohyun,Cheng, Shengxian,Feng, Weijin,He, Jun,Hu, Jieying,Xin, Yinger,Xu, Zhengtao,Zeller, Matthias
, p. 5757 - 5763 (2021/05/04)
The infusion of metal guests into (i.e., metalating) the porous medium of metal-organic frameworks (MOFs) is a topical approach to wide-ranging functionalization purposes. We report the notable interactions of AgSbF6 guests with the designer MOF host ZrL1 [Zr6O4(OH)7(L1)4.5(H2O)4]. (1) The heavy-atom guests of AgSbF6 induce order in the MOF host to allow the movable alkyne side arm to be fully located by X-ray diffraction, but they themselves curiously remain highly disordered and absent in the strucutral model. The enhanced order of the framework can be generally ascribed to interaction of the silver guests with the host alkyne and thioether functions, while the invisible heavy-atom guest represents a new phenomenon in the metalation of open framework materials. (2) The AgSbF6 guests also participate in the thermocyclization of the vicinal alkyne units of the L1 linker (at 450 °C) and form the rare nanoparticle of Ag3Sb supported on the concomitantly formed nanographene network. The resulted composite exhibits high electrical conductivity (1.0 S/cm) as well as useful, mitigated catalytic activity for selectively converting nitroarenes into the industrially important azo compounds, i.e., without overshooting to form the amine side products. The heterogeneous/cyclable catalysis entails only the cheap reducing reagents of NaBH4, ethanol, and water, with yields being generally close to 90%.
Highly Chemoselective Reduction of Nitroarenes Using a Titania-Supported Platinum-Nanoparticle Catalyst under a CO Atmosphere
Li, Shushuang,Wang, Fuzerong,Liu, Yongmei,Cao, Yong
, p. 591 - 595 (2017/05/29)
The discovery that supported gold catalysts can promote CO/H2O-mediated reduction at ambient temperatures is important to chemoselective synthesis and has gained significant attention in recent years. Whether the alternative Pt group metal (PGM) catalysts can exhibit such exceptional performance is thus an interesting research issue. So far, no PGM catalyst shows activity for CO/H2O-mediated reduction at ambient temperatures. Here, we demonstrate that it is possible to transform nonactive into highly active and selective catalysts for CO/H2O-mediated reduction by modulating the interfacial structure and electronic properties at the metal-support interfaces. Thus, highly active and chemoselective hydrogenation Pt, Ir, Rh and Pd catalysts can be prepared by decorating the exposed metal faces with partially reduced support species by means of a simple catalyst activation procedure. In this way, it has been possible to dramatically facilitate the previously unappreciated PGM-catalyzed activation of CO molecules under mild conditions, which can make a significant contribution not only to reveal the intrinsic catalytic potential of supported PGMs but also to establish a more sustainable and industrially-relevant process.
Sodium Arenetellurolate Catalyzed Selective Conversion of Nitroaromatics to Aromatic Azoxy or Azo Compounds and Its Application for Facile Preparation of 3,3'- and 4,4'-Bisazobenzenes from (3- and 4-Nitrophenyl)acetylenes
Ohe, Kouichi,Uemura, Sakae,Sugita, Nobuyuki,Masuda, Hideki,Taga, Toru
, p. 4169 - 4174 (2007/10/02)
Treatment of aromatic nitro compounds with sodium borohydride in alkaline ethanol in the presence of a catalytic amount of diaryl ditelluride at room temperature affords the corresponding azoxy compounds selectively in fair to excellent yields.Under reflux aromatic azo compounds are obtained as major products.In situ generated sodium arenetellurolate (ArTeNa) is the active species to reduce nitroaromatics into aromatic nitroso compounds, the latter being easily converted into azoxy compounds in alkaline ethanol.Higher temperature enables ArTeNa to reduce the initially produced azoxy compounds into azo compounds.A new vinylic telluride having an azo group in the molecule, 3,3'-bisazobenzene, was prepared in one pot in 66-91percent isolated yield by treating (3-nitrophenyl)acetylene with a stoichiometric amount of ArTeNa in alkaline ethanol at reflux temperature, the structure of which was determined unambiguously by X-ray crystallography.The corresponding 4, 4'-isomer was similarly prepared, but in lower yield.