The Experts below are selected from a list of 963 Experts worldwide ranked by ideXlab platform

Khadijah M. Al-zaydi - One of the best experts on this subject based on the ideXlab platform.

O. Reynes - One of the best experts on this subject based on the ideXlab platform.

  • Electrocatalytic carboxylation of Chloroacetonitrile mediated by a Co(I) phenanthroline complex: Mechanistic and spectroscopic studies
    Journal of Electroanalytical Chemistry, 2013
    Co-Authors: P.-l. Fabre, Dancheng Chen, O. Reynes, Nadia Chouini-lalanne, Valérie Sartor
    Abstract:

    Abstract Mechanisms implied in the electrocarboxylation of Chloroacetonitrile (Cl–CH 2 –CN, noted RCl) mediated by [Co(II)(phen) 3 ] 2+ have been investigated by cyclic voltammetry and spectroelectrochemistry (UV–Visible and e.p.r.). The studies showed that the oxidative addition of Chloroacetonitrile on the electrogenerated [Co(I)(phen) 2 ] + yields an alkyl-cobalt R-Co(III) complex. This complex can either be reduced into an alkyl-cobalt(II) or undergoes a homolytic cobalt–carbon bond cleavage to form the organic radical R and the [Co(II)(phen) 2 ] 2+ complex. Whatever the process, R − and [Co(I)(phen) 2 ] + were produced. In presence of free phenanthroline, the catalytic behaviour of the complex was strongly vanished because the formation of the active complex [Co(I)(phen) 2 ] + is restricted. Under CO 2 atmosphere, the catalytic electrocarboxylation of Chloroacetonitrile was observed. Bulk electrolyses showed that the carboxylated and faradic yields depended on the applied electrolysis potential and free phenanthroline concentration.

  • Electrocarboxylation of Chloroacetonitrile by a Cobalt(I) complex of terpyridine
    Electrochimica Acta, 2011
    Co-Authors: Dancheng Chen, P.-l. Fabre, O. Reynes
    Abstract:

    The electrocarboxylation of Chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with Chloroacetonitrile. The oxidative addition of Chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of Chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions.

  • Electrocarboxylation of Chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
    Elsevier, 2010
    Co-Authors: P.-l. Fabre, O. Reynes
    Abstract:

    The electrocarboxylation of Chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates Chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of Chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen). Keywords: Electrocarboxylation, Cobalt tris (phenanthroline), Electrocatalysis, Chloroacetonitrile, Cyanoacetic aci

  • Electrocarboxylation of Chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
    Electrochemistry Communications, 2010
    Co-Authors: P.-l. Fabre, O. Reynes
    Abstract:

    Abstract The electrocarboxylation of Chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates Chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of Chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen).

Mohsin Ahmad Bhat - One of the best experts on this subject based on the ideXlab platform.

  • Ionic Liquid Induced Enhancement in the Stickiness of Sticky Dissociative Electroreductive CCl Bond Cleavage: A Key to Eco-Green Detoxification of Chloroacetonitrile
    Electrochimica Acta, 2016
    Co-Authors: Sarwar Ahmad Pandit, Mudasir Ahmad Rather, Sajad Ahmad Bhat, Khaliquz Zaman Khan, Pravin P. Ingole, Mohsin Ahmad Bhat
    Abstract:

    Abstract Detailed voltammetric investigations that demonstrate the potential of 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM][BF 4 ]), a commonly used room-temperature ionic liquid (RTIL), to enhance the stickiness in the sticky dissociative electrodetoxification pathway for Chloroacetonitrile are presented. Convolution analysis of the voltammetric data in light of the Marcus-Hush formulation reveals that electroreductive cleavage of the C Cl bond of Chloroacetonitrile (ClCH 2 CN) in [BMIM][BF 4 ] follows a sticky dissociative pathway like that in conventional organic solvents. Interestingly the interaction energy between Cl and CNCH 2 (radical) in [BMIM][BF 4 ] is observed to be almost ten times higher than that reported for the same species in N,N -dimethylformamide (DMF). This RTIL-induced enhancement in the interaction energy among the electrochemically generated fragments reduces the kinetic barrier and hence the overpotential required for heterogeneous electroreduction of ClCH 2 CN. The lower overpotential that implies lesser energy consumption for the electroreduction and the green features of [BMIM][BF 4 ] jointly support the use of imidazolium-based RTILs for eco-green electrodetoxification of halohydrocarbons like Chloroacetonitrile.

P.-l. Fabre - One of the best experts on this subject based on the ideXlab platform.

  • Electrocatalytic carboxylation of Chloroacetonitrile mediated by a Co(I) phenanthroline complex: Mechanistic and spectroscopic studies
    Journal of Electroanalytical Chemistry, 2013
    Co-Authors: P.-l. Fabre, Dancheng Chen, O. Reynes, Nadia Chouini-lalanne, Valérie Sartor
    Abstract:

    Abstract Mechanisms implied in the electrocarboxylation of Chloroacetonitrile (Cl–CH 2 –CN, noted RCl) mediated by [Co(II)(phen) 3 ] 2+ have been investigated by cyclic voltammetry and spectroelectrochemistry (UV–Visible and e.p.r.). The studies showed that the oxidative addition of Chloroacetonitrile on the electrogenerated [Co(I)(phen) 2 ] + yields an alkyl-cobalt R-Co(III) complex. This complex can either be reduced into an alkyl-cobalt(II) or undergoes a homolytic cobalt–carbon bond cleavage to form the organic radical R and the [Co(II)(phen) 2 ] 2+ complex. Whatever the process, R − and [Co(I)(phen) 2 ] + were produced. In presence of free phenanthroline, the catalytic behaviour of the complex was strongly vanished because the formation of the active complex [Co(I)(phen) 2 ] + is restricted. Under CO 2 atmosphere, the catalytic electrocarboxylation of Chloroacetonitrile was observed. Bulk electrolyses showed that the carboxylated and faradic yields depended on the applied electrolysis potential and free phenanthroline concentration.

  • Electrocarboxylation of Chloroacetonitrile by a Cobalt(I) complex of terpyridine
    Electrochimica Acta, 2011
    Co-Authors: Dancheng Chen, P.-l. Fabre, O. Reynes
    Abstract:

    The electrocarboxylation of Chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with Chloroacetonitrile. The oxidative addition of Chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of Chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions.

  • Electrocarboxylation of Chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
    Elsevier, 2010
    Co-Authors: P.-l. Fabre, O. Reynes
    Abstract:

    The electrocarboxylation of Chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates Chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of Chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen). Keywords: Electrocarboxylation, Cobalt tris (phenanthroline), Electrocatalysis, Chloroacetonitrile, Cyanoacetic aci

  • Electrocarboxylation of Chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
    Electrochemistry Communications, 2010
    Co-Authors: P.-l. Fabre, O. Reynes
    Abstract:

    Abstract The electrocarboxylation of Chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates Chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of Chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen).

Christian Bruneau - One of the best experts on this subject based on the ideXlab platform.