Autoxidation von CuI-Komplexen,VI: Kinetischer Nachweis instabiler Sauerstoffaddukte bei der Oxidation von solvatisiertem Cu+ in Dimethylsulfoxid
The interaction between Cu+ and O2 has been studied in DMSO. The experimental rate law is given by −d[O2]/dt = kter [Cu+]2[O2](1 + kH[H+]) with kter = (7.1 ± 0.4)・103 M-2s-1and kH = 190 ± 12 M-1 at 25° and l=0.1.The redox-stoichiometry O2 : Cu+ is strictly 1:2 but less than one third of the metal...
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| Main Authors: | , |
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| Format: | Article |
| Language: | deu |
| Published: |
Swiss Chemical Society
1974-02-01
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| Series: | CHIMIA |
| Online Access: | https://www.chimia.ch/chimia/article/view/9126 |
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| Summary: | The interaction between Cu+ and O2 has been studied in DMSO. The experimental rate law is given by −d[O2]/dt = kter [Cu+]2[O2](1 + kH[H+]) with kter = (7.1 ± 0.4)・103 M-2s-1and kH = 190 ± 12 M-1 at 25° and l=0.1.The redox-stoichiometry O2 : Cu+ is strictly 1:2 but less than one third of the metal ion was present as ESR active Cu2+ in fully reacted aprotic mixtures. Neither H2O2 nor O2- could be identified in such solutions. Full amounts of Cu2+ and H2O2 are found in DMSO acidified by H2SO4 or HClO4, however. The results have to be explained by the formation of at least two different unstable dioxygen adducts, one probably being binuclear Cu2O22+, and spin coupled Cu2+ dimers or polymers with the reaction product of O22- and DMSO as ligand.
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| ISSN: | 0009-4293 2673-2424 |