Bridging the Gap between Electrochemical and Organometallic Activation: Benzyl Chloride Reduction at Silver Cathodes.
Integration of voltammetry, surface-enhanced Raman spectroscopy (SERS), and density functional theory (DFT) has allowed unraveling the mechanistic origin of the exceptional electrocatalytic properties of silver cathodes during the reduction of benzyl chloride. At inert electrodes the initial reducti...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 48; pp. 17199 - 17211 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
12/8/2010
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=57332103&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 57332103 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/8/2010 vid: 132 iid: 48 pid: 997 pub: American Chemical Society artinfo: ui: 57332103 10.1021/ja106049c ppf: 17199 ppct: 12 formats: tig: atl: Bridging the Gap between Electrochemical and Organometallic Activation: Benzyl Chloride Reduction at Silver Cathodes. aug: au: Yi-Fan Huang De-Yin Wu An Wang Bin Ren Rondinini, Sandra Zhong-Qun Tian Amatore, Christian affil: State Key Laboratory of Physical Chemistry of Solid Surfaces and College of Chemistry and Chemical Engineering, Xiamen University, 361005 Xiamen, China Dipartimento di Chimica Fisica ed Elettrochimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milan; Italy Département de Chimie, Ecole Normale Supérieure, UMR 8640, 24 Rue Lhomond, F-75231 Paris Cedex 5, France su: Organometallic chemistry Transition metal complexes Voltammetry Raman spectroscopy Density functionals Silver Cathodes sug: subj: Organometallic chemistry Transition metal complexes Voltammetry Raman spectroscopy Density functionals Silver Cathodes ab: Integration of voltammetry, surface-enhanced Raman spectroscopy (SERS), and density functional theory (DFT) has allowed unraveling the mechanistic origin of the exceptional electrocatalytic properties of silver cathodes during the reduction of benzyl chloride. At inert electrodes the initial reduction proceeds through a concerted direct electron transfer yielding a benzyl radical as the first intermediate. Conversely, at silver electrodes it involves an uphill preadsorption of benzyl chloride onto the silver cathode. Reduction of this adduct affords a species tentatively described as a distorted benzyl radical anion stabilized by the silver surface. This transient species rapidly evolves to yield ultimately a benzyl radical bound onto the silver surface, the latter being reduced into a benzyl-silver anionic adduct which eventually dissociates into a free benzyl anion at more negative potentials. Within this framework, the exceptional electrocatalytic properties of silver cathodes stem from the fact that they drastically modify the mechanism of the 2e-reduction pathway through a direct consequence of the electrophilicity of silver cathode surfaces toward organic halides. This mechanism contrasts drastically with any of those tentatively invoked previously, and bridges classical electroreduction mechanisms and oxidative additions similar to those occurring during organometallic homogeneous activation of organic halides by low-valent transition-metal complexes. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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