Catalytic dioxygen reduction mediated by a tetranuclear cobalt complex supported on a stannoxane core
| dc.contributor.author | Chandra, Anirban | |
| dc.contributor.author | Mebs, Stefan | |
| dc.contributor.author | Kundu, Subrata | |
| dc.contributor.author | Kuhlmann, Uwe | |
| dc.contributor.author | Hildebrandt, Peter | |
| dc.contributor.author | Dau, Holger | |
| dc.contributor.author | Ray, Kallol | |
| dc.date.accessioned | 2021-06-10T07:50:28Z | |
| dc.date.available | 2021-06-10T07:50:28Z | |
| dc.date.issued | 2020-04-08 | |
| dc.description.abstract | The synthesis, spectroscopic characterization (infrared, electron paramagnetic resonance and X-ray absorption spectroscopies) and density functional theoretical calculations of a tetranuclear cobalt complex Co4L1 involving a nonheme ligand system, L1, supported on a stannoxane core are reported. Co4L1, similar to the previously reported hexanuclear cobalt complex Co6L2, shows a unique ability to catalyze dioxygen (O2) reduction, where product selectivity can be changed from a preferential 4e−/4H+ dioxygen-reduction (to water) to a 2e−/2H+ process (to hydrogen peroxide) only by increasing the temperature from −50 to 30 °C. Detailed mechanistic insights were obtained on the basis of kinetic studies on the overall catalytic reaction as well as by low-temperature spectroscopic (UV-Vis, resonance Raman and X-ray absorption spectroscopies) trapping of the end-on μ-1,2-peroxodicobalt(III) intermediate 1. The Co4L1- and Co6L2-mediated O2-reduction reactions exhibit different reaction kinetics, and yield different ratios of the 2e−/2H+ and 4e−/4H+ products at −50 °C, which can be attributed to the different stabilities of the μ-1,2-peroxodicobalt(III) intermediates formed upon dioxygen activation in the two cases. The deep mechanistic insights into the transition-metal mediated dioxygen reduction process that are obtained from the present study should serve as useful and broadly applicable principles for future design of more efficient catalysts in fuel cells. | en |
| dc.description.sponsorship | DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat" | en |
| dc.identifier.eissn | 1477-9234 | |
| dc.identifier.issn | 1477-9226 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/13232 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-12027 | |
| dc.language.iso | en | en |
| dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | en |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.subject.other | catalytic dioxygen reduction | en |
| dc.subject.other | tetranuclear cobalt complex | en |
| dc.subject.other | stannoxane core | en |
| dc.title | Catalytic dioxygen reduction mediated by a tetranuclear cobalt complex supported on a stannoxane core | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1039/D0DT00475H | en |
| dcterms.bibliographicCitation.issue | 18 | en |
| dcterms.bibliographicCitation.journaltitle | Dalton Transactions | en |
| dcterms.bibliographicCitation.originalpublishername | Royal Society of Chemistry | en |
| dcterms.bibliographicCitation.originalpublisherplace | Cambridge | en |
| dcterms.bibliographicCitation.pageend | 6073 | en |
| dcterms.bibliographicCitation.pagestart | 6065 | en |
| dcterms.bibliographicCitation.volume | 49 | en |
| tub.accessrights.dnb | free | en |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Physikalische Chemie / Biophysikalische Chemie | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.group | FG Physikalische Chemie / Biophysikalische Chemie | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin | en |