Intramolecular Redox-Active Ligand-to-Substrate Single-Electron Transfer: Radical Reactivity with a Palladium(II) Complex
| Authors |
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| Publication date | 2014 |
| Journal | Journal of the American Chemical Society |
| Volume | Issue number | 136 | 33 |
| Pages (from-to) | 11574-11577 |
| Organisations |
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| Abstract | Coordination of the redox-active tridentate NNO ligand L-H2 to Pd-II yields the paramagnetic iminobenzosemiquinonato complex 3. Single-electron reduction of 3 yields diamagnetic amidophenolato complex 4, capable of activating aliphatic azide 5. Experimental and computational studies suggest a redox-noninnocent pathway wherein the redox-active ligand facilitates intramolecular ligand-to-substrate single-electron transfer to generate an open-shell singlet "nitrene-substrate radical, ligand radical", enabling subsequent radical-type C-H amination reactivity with Pd-II. |
| Document type | Article |
| Note | With supporting information |
| Language | English |
| Published at |
https://doi.org/10.1021/ja502164f
(Final published version)
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