72-54-8Relevant articles and documents
Design of a bimetallic Au/Ag system for dechlorination of organochlorides: Experimental and theoretical evidence for the role of the cluster effect
Romashov, Leonid V.,Khemchyan, Levon L.,Gordeev, Evgeniy G.,Koshevoy, Igor O.,Tunik, Sergey P.,Ananikov, Valentine P.
, p. 6003 - 6012 (2014)
The experimental study of dechlorination activity of a Au/Ag bimetallic system has shown formation of a variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratios from 1:1 to 4:1. It is the formation of the Au/Ag cluster species that mediated C-Cl bond breakage, since neither Au nor Ag species alone exhibited a comparable activity. The nature of the products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, NMR, and quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that formation of bimetallic clusters facilitated dechlorination activity due to the thermodynamic factor: C-Cl bond breakage by metal clusters was thermodynamically favored and resulted in the formation of chlorinated bimetallic species. An appropriate Au:Ag ratio for an efficient hydrodechlorination process was determined in a joint experimental and theoretical study carried out in the present work. This mechanistic finding was followed by synthesis of molecular bimetallic clusters, which were successfully involved in the hydrodechlorination of CCl4 as a low molecular weight environment pollutant and in the dechlorination of dichlorodiphenyltrichloroethane (DDT) as an eco-toxic insecticide. High activity of the designed bimetallic system made it possible to carry out a dechlorination process under mild conditions at room temperature.
Photosensitizing catalysis of the B12 complex without an additional photosensitizer
Shimakoshi, Hisashi,Li, Li,Nishi, Masashi,Hisaeda, Yoshio
, p. 10921 - 10923 (2011)
A cobalamin derivative, heptamethyl cobyrinate perchlorate, was activated by UV light irradiation to form a Co(i) species in the presence of triethanolamine and used for a dechlorination reaction, and this photochemical reaction was accelerated in an ionic liquid.
A polymerized ionic liquid-supported B12 catalyst with a ruthenium trisbipyridine photosensitizer for photocatalytic dechlorination in ionic liquids
Zhang, Wei,Shimakoshi, Hisashi,Houfuku, Noriyuki,Song, Xi-Ming,Hisaeda, Yoshio
, p. 13972 - 13978 (2014)
By immobilizing a B12 complex and a Ru(ii) trisbipyridine photosensitizer in a polymerized ionic liquid (PIL), a visible light-driven photocatalyst was developed. The synthesized copolymer was characterized by GPC and DLS, and using UV-vis absorption spectra and luminescence spectra. The Ru(ii) trisbipyridine photosensitizer in the copolymer showed an enhanced emission compared to that of the monomer in the ionic liquid, 1-butyl-4-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C 4mim][NTf2]). Formation of the Co(i) species of the B 12 complex in the copolymer was confirmed by the UV-vis spectral change in [C4mim][NTf2] containing a sacrificial reductant (triethanolamine) under irradiation with visible light. The copolymer showed a high photocatalytic activity in various ionic liquids for 1,1-bis(4- chlorophenyl)-2,2,2-trichloroethane (DDT) dechlorination with ~99% conversion after visible light irradiation for 2 h. Furthermore, both the B 12 catalyst and photosensitizer in the polymer were easily recycled for use with the ionic liquid solvent without any loss of catalytic activity.
Synthesis of a B12-BODIPY dyad for B12-inspired photochemical transformations of a trichloromethylated organic compound
Anai, Yuki,Shichijo, Keita,Fujitsuka, Mamoru,Hisaeda, Yoshio,Shimakoshi, Hisashi
supporting information, p. 11945 - 11948 (2020/10/15)
A B12complex-BODIPY dyad was synthesized by peripheral modification of cobalamin derivatives. The photophysical properties of the dyad were investigated by UV-vis, PL, and transient absorption spectroscopy. A visible light-driven dechlorination reaction of a trichlorinated organic compound, DDT, was reported. The dyad showed efficient catalysis for dechlorination under N2with turnover numbers of over 220 for the reaction. One-pot syntheses of an ester and amide from DDT and benzotrichloride were also achieved using the dyad under air.
Photocatalytic function of the B12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation
Tian, Hui,Shimakoshi, Hisashi,Park, Gyurim,Kim, Sinheui,You, Youngmin,Hisaeda, Yoshio
, p. 675 - 683 (2018/02/16)
A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(iii) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6) as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(ii)(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, i.e., the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that the oxidative quenching of the photosensitizer dominated over the reductive quenching pathway.