23691-27-2Relevant articles and documents
Radical reactions catalysed by homobimetallic ruthenium(II) complexes bearing Schiff base ligands: Atom transfer radical addition and controlled polymerisation
De Clercq, Bob,Verpoort, Francis
, p. 4687 - 4690 (2002)
The homobimetallic ruthenium Schiff base complexes Ia-f mediated the atom transfer radical addition (ATRA) of carbon tetrachloride across olefins in excellent yields which markedly depended on the catalyst and the substrate used. The best catalytic system Ic is able to compete with the highest performing ruthenium catalysts reported so far for ATRA reactions. In addition these systems are also capable of performing atom transfer radical polymerisation (ATRP) reactions with styrene in high yields and with good control over molecular weight and molecular weight distribution.
Microwave-enhanced ruthenium-catalysed atom transfer radical additions
Borguet, Yannick,Richel, Aurore,Delfosse, Sébastien,Leclerc, Alain,Delaude, Lionel,Demonceau, Albert
, p. 6334 - 6338 (2007)
The first monomode microwave-assisted atom transfer radical additions (ATRA) of carbon tetrachloride to various olefins were successfully performed, affording the adducts with almost quantitative yields in less than 10 min at 160 °C.
New pincer-type diphosphinito (POCOP) complexes of NiII and NiIII
Pandarus, Valerica,Zargarian, Davit
, p. 978 - 980 (2007)
This communication reports the synthesis and characterization of the new, pincer-type, square-planar, 16-electron compounds {2,6-(OPPri 2)2C6H3}NiIIBr, 1, and {(Pri2POCH2)2CH}NiIIBr, 2, and the square-pyramidal, 17-electron complex {(Pri 2POCH2)2CH}NiIIIBr2, 3. The Royal Society of Chemistry.
31Cl NQR SPECTRA OF COMPOUNDS IN Cl3CCH2CXRR' SERIES
Feshin, V. P.,Dolgushin, G. V.,Voronkov, M. G.,Gaek, M.,Yanoushek, Z.
, p. 684 - 687 (1990)
In molecules in the series Cl3CCH2CClRR', the substituents R and R' virtually do not affect the chlorine atoms of the Cl3C group, while the NQR frequency of the chlorine atom of the CClRR' group correlates satisfactorily with the ?* constants of these substituents.The regularities observed in the mutual influence of the atoms in the molecules of the studied series indicate that the previously assumed structure of some products of radical telomerization of Cl3CH with H2C=CHCl is erroneous.
Kharasch addition catalysed by half-sandwich ruthenium complexes. Enhanced activity of ruthenacarboranes
Tutusaus, Oscar,Delfosse, Sébastien,Demonceau, Albert,Noels, Alfred F.,Vi?as, Clara,Teixidor, Francesc
, p. 8421 - 8425 (2003)
Ruthenium complexes of the type [RuH(η5-CB)(PPh 3)2] {CB is a monoanionic charge-compensated carborane ligand such as [9-SR2-7,8-C2B9H 10]- and [9-SR2-7-CH3-7,8-C 2B9H9]-} efficiently catalyse the Kharasch addition of CCl4 across olefins and, with maximum total turnover numbers of 9000 and initial turnover frequencies of 1900 h -1 at 40°C, highly surpass their Ru-Cp# analogues in these reactions.
New, highly efficient catalyst precursors for Kharasch additions - [RuCl(Cp*)(PPh3)2] and [RuCl(Ind)(PPh3)2]
Simal, Fran?ois,Wlodarczak, Lise,Demonceau, Albert,Noels, Alfred F.
, p. 2689 - 2695 (2001)
[RuCl(Cp*)(PPh3)2] and [RuCl(Ind)(PPh3)2] are excellent catalyst precursors for promoting the Kharasch addition of CCl4 and CHCl3 across olefins under mild reaction conditions (at temperatures as low as 40 °C with CCl4). The effect of the substituents on the cyclopentadienyl ring has been investigated. In terms of efficiency and activity, [RuCl(Cp*)(PPh3)2] and [RuCl(Ind)(PPh3)2] surpass the best ruthenium systems reported so far. A two-step mechanism, in which the extrusion of a phosphane ligand occurs prior to the activation of the halogenated compound by the unsaturated ruthenium center, is suggested.
Bimolecular concerted elimination as an elementary stage in free-radical reactions. Reaction of organocobaloximes with bromotrichloromethane
Dneprovskii,Kasatochkin
, p. 1444 - 1450 (2001)
In free-radical reaction of cis-β-phenylvinylcobaloxime with bromotrichloromethane the primary product, phenylacetylene, arises as a result of elimination, and further it adds the bromotrichloromethane. Similarly proceeds the reaction between β-phenylethylcobaloxime with bromotrichloromethane. The values of absolute rate constants and their relation to the nature of the axial ligand completely agree with the assumption that in the reactions in question similarly to the E2 mechanism of nucleophilic elimination the elimination occurs as one-stage bimolecular process with the simultaneous rupture of C-Co and C-H bonds.
Cycloruthenated complexes as homogeneous catalysts for atom-transfer radical additions
Parkhomenko, Ksenia,Barloy, Laurent,Sortais, Jean-Baptiste,Djukic, Jean-Pierre,Pfeffer, Michel
, p. 822 - 825 (2010)
Various cycloruthenated complexes were used as homogeneous catalysts for the atom-transfer radical addition of polyhalogenated compounds to several olefinic substrates. Yields obtained through conventional or microwave heating could reach high values (up to 98% with CBrCl3 and 88% with CCl4).
Radical reactions catalysed by ruthenium(II) complexes with anionic carborane phosphine ligands: Kharasch addition to olefins and controlled polymerisation
Simal, Fran?ois,Sebille, Sophie,Demonceau, Albert,Noels, Alfred F.,Nu?ez, Rosario,Abad, Mar,Teixidor, Francesc,Vi?as, Clara
, p. 5347 - 5351 (2000)
Ruthenium-carborane complexes 1-3 mediated the Kharasch addition of carbon tetrachloride across olefins with high yields which markedly depended on the catalyst and the substrate used. In addition, the atom transfer radical polymerisation of methyl methacrylate could be carried out in a highly controlled way. (C) 2000 Elsevier Science Ltd.
Cu-Catalyzed photoredox chlorosulfonation of alkenes and alkynes
Alkan-Zambada, Murat,Hu, Xile
, p. 4525 - 4533 (2019/04/25)
Visible-light photoredox chlorosulfonation of alkenes and alkynes is achieved using a Cu photocatalyst. The reactions occur under mild conditions, have broad scope, and have high functional group tolerance.
Atom Transfer Radical Addition Catalyzed by Ruthenium-Arene Complexes Bearing a Hybrid Phosphine-Diene Ligand
Chotard, Florian,Malacea-Kabbara, Raluca,Balan, Cédric,Bodio, Ewen,Picquet, Michel,Richard, Philippe,Ponce-Vargas, Miguel,Fleurat-Lessard, Paul,Le Gendre, Pierre
, p. 812 - 820 (2018/03/21)
The synthesis and characterization of a series of arene ruthenium complexes bearing either (3,5-cycloheptadienyl)diphenylphosphine or (cycloheptyl)diphenylphosphine are reported. Upon irradiation or heating, all these complexes lose their arene ligand but then exhibit a different behavior depending on the nature of the phosphine ligand. (Cycloheptadienyl)phosphine complexes 1 and 3 give a cationic dinuclear Ru complex 5 for which the two Ru atoms are bridged by three chlorido ligands and flanked by two tridendate (cycloheptadienyl)phosphines. (Cycloheptyl)diphenylphosphine complexes 2 and 4 undergo arene exchange when toluene is used as solvent or degrade in dichloromethane. ATRA catalytic trials conducted in parallel with these complexes using CCl4 and styrene as standard substrates, highlighted the deep impact of the dienyl moiety on the results. Under smooth conditions (UV irradiation or moderate heating), only (cycloheptyl)phosphine derivatives give Karasch adduct in satisfactory yields. Their performance was considerably improved by combining irradiation and heating. At higher temperature, cationic dinuclear complex 5 was revealed as active and robust, giving turnover numbers as high as 9700 when tetradecene and CCl4 were used as substrates.