Peroxocobalt(iii) species activates nitriles via a superoxocobalt(ii) diradical state
The dioxygenation of nitriles by [CoIII(TBDAP)(O2)]+ (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations. The mechanism proposed previously based on experimental observations, which invoked an outer-sphere cycloaddition, was found to be unreasonable. Instead, calculations suggest that an inner-sphere mechanism involving the cleavage of one of the Co-O bonds assisted by substrate uptake is much more likely. The reactively competent species is a triplet consisting of a Co(ii)-superoxo functionality, which can undergo O-C bond formation and O-O bond cleavage traversing low energy transition states. The role of the structurally rigid TBDAP ligand is to prevent the participation of the pyridyl ligand in the delocalization of the unpaired electron density.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:49 |
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| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 49(2020), 9 vom: 03. März, Seite 2819-2826 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Cho, Dasol [VerfasserIn] |
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| Anmerkungen: |
Date Completed 03.03.2020 Date Revised 03.03.2020 published: Print Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1039/d0dt00042f |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM305588885 |
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| 500 | |a Date Revised 03.03.2020 | ||
| 500 | |a published: Print | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The dioxygenation of nitriles by [CoIII(TBDAP)(O2)]+ (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations. The mechanism proposed previously based on experimental observations, which invoked an outer-sphere cycloaddition, was found to be unreasonable. Instead, calculations suggest that an inner-sphere mechanism involving the cleavage of one of the Co-O bonds assisted by substrate uptake is much more likely. The reactively competent species is a triplet consisting of a Co(ii)-superoxo functionality, which can undergo O-C bond formation and O-O bond cleavage traversing low energy transition states. The role of the structurally rigid TBDAP ligand is to prevent the participation of the pyridyl ligand in the delocalization of the unpaired electron density | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Choi, Seulhui |e verfasserin |4 aut | |
| 700 | 1 | |a Cho, Jaeheung |e verfasserin |4 aut | |
| 700 | 1 | |a Baik, Mu-Hyun |e verfasserin |4 aut | |
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