The Homogeneous Reduction of CO by [Ni(cyclam)]: Increased Catalytic Rates with the Addition of a CO Scavenger.
The homogeneous electrochemical reduction of CO by the molecular catalyst [Ni(cyclam)] is studied by electrochemistry and infrared spectroelectrochemistry. The electrochemical kinetics are probed by varying CO substrate and proton concentrations. Products of CO reduction are observed in infrared spe...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 10; pp. 3565 - 3574 |
|---|---|
| Autores principales: | , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
3/18/2015
|
| 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=101913649&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 101913649 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: 3/18/2015 vid: 137 iid: 10 pid: 997 pub: American Chemical Society artinfo: ui: 101913649 10.1021/ja512575v ppf: 3565 ppct: 9 formats: tig: atl: The Homogeneous Reduction of CO by [Ni(cyclam)]: Increased Catalytic Rates with the Addition of a CO Scavenger. aug: au: Froehlich, Jesse D. Kubiak, Clifford P. affil: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, United States su: Chemical reduction Catalysts Electrochemistry Chemical species Bicarbonate ions Macrocyclic compounds Density functional theory sug: subj: Chemical reduction Catalysts Electrochemistry Chemical species Bicarbonate ions Macrocyclic compounds Density functional theory ab: The homogeneous electrochemical reduction of CO by the molecular catalyst [Ni(cyclam)] is studied by electrochemistry and infrared spectroelectrochemistry. The electrochemical kinetics are probed by varying CO substrate and proton concentrations. Products of CO reduction are observed in infrared spectra obtained from spectroelectrochemical experiments. The two major species observed are a Ni(I) carbonyl, [Ni(cyclam)(CO)], and a Ni(II) coordinated bicarbonate, [Ni(cyclam)(COOH)]. The rate-limiting step during electrocatalysis is determined to be CO loss from the deactivated species, [Ni(cyclam)(CO)], to produce the active catalyst, [Ni(cyclam)]. Another macrocyclic complex, [Ni(TMC)], is deployed as a CO scavenger in order to inhibit the deactivation of [Ni(cyclam)] by CO. Addition of the CO scavenger is shown to dramatically increase the catalytic current observed for CO reduction. Evidence for the [Ni(TMC)] acting as a CO scavenger includes the observation of [Ni(TMC)(CO)] by IR. Density functional theory (DFT) calculations probing the optimized geometry of the [Ni(cyclam)(CO)] species are also presented. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
|---|