Xn:Harmful;821-55-6Relevant articles and documents
Ru(iii) -based polyoxometalate tetramers as highly efficient heterogeneous catalysts for alcohol oxidation reactions at room temperature
Li, Huafeng,Ma, Pengtao,Niu, Jingyang,Song, Junpeng,Wang, Jingping,Wang, Yaqiong,Zhao, Xue,Zou, Yan
, p. 12664 - 12673 (2021/09/28)
A novel ruthenium-containing polyoxometalate-based organic-inorganic hybrid, K4Na9H7.4[(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]·42H2O (1), was successfully synthesized by a one-step hydrothermal method under acidic conditions, which applied a self-assembly strategy between inorganic polyoxometalate based on trivacant [B-α-AsW9O33]9?{AsW9} fragments and an organic ligand, imidazole (C3H4N2). Compound1was further characterized by single-crystal X-ray diffraction, PXRD, IR spectroscopy, UV-Vis spectroscopy, ESI-MS, elemental analysis and TGA. Single-crystal X-ray diffraction data reveal that the polyanion consists of four trivacant Keggin-type polyanion {AsW9} building blocks bridged by four {WO6} units, leading to a crown-shaped tetrameric structure [(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]20.4?. The ESI-MS result reveals that the polyanion unit has excellent structural integrity in water. Moreover, the catalysis study of1was also further investigated, and the experimental results indicate heterogeneous catalyst1presents high efficiency (yield = 98%), excellent selectivity (>99%), and good recyclability for the oxidation of 1-(4-chlorophenyl)ethanol to 4′-chloroacetophenone with commercially available 70% aqueoustert-butyl hydroperoxide {TBHP (aq.)} as the oxidant at room temperature.
The effect of the position of cross-linkers on the structure and microenvironment of PPh3moiety in porous organic polymers
Ji, Guangjun,Li, Cunyao,Xiao, Dong,Wang, Guoqing,Sun, Zhao,Jiang, Miao,Hou, Guangjin,Yan, Li,Ding, Yunjie
, p. 9165 - 9174 (2021/04/16)
Three trivinyl functionalization triphenylphosphine (3vPPh3)-based porous organic ligands (3vPPh3-POLs) with cross-linkers in different positions were obtained through solvothermal polymerization. By simply changing the position of the cross-linkers (vinyl groups) attached to the PPh3monomer, the resulting porous organic polymer (POP) materials acquired diverse hierarchical porous structures, and the microenvironment of POPs was sequently regulated. Among the three 3vPPh3-POLs, the BET surface areas ranged from 168 to 1583 m2g?1, while the proportion of micropores changed from 0.0% to 52.0%. Benefiting from the unique structure, Rh ions could be coordinated and dispersed as a single site inm-3vPPh3-POL to form HRh(CO)2(PPh3-POL)2species, which endowed the Rh/m-3vPPh3-POL catalyst with an activity similar to that in the homogeneous system, anl/bratio (the ratio of the linear aldehyde to the branched aldehyde) approximately as high as 10, and stability for a duration of more than 500 h in the hydroformylation of 1-octene.
Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones
Beltran, Frédéric,Bergamaschi, Enrico,Funes-Ardoiz, Ignacio,Teskey, Christopher J.
supporting information, p. 21176 - 21182 (2020/09/17)
Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
