Nitrene Photochemistry of Manganese N-Haloamides*
© 2021 Wiley-VCH GmbH..
Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C-H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1 H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C-H bonds, such as the α-C-H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C-H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn-N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N-I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:60 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 60(2021), 51 vom: 13. Dez., Seite 26647-26655 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Van Trieste, Gerard P [VerfasserIn] |
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| Links: |
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| Themen: |
C−H Amination |
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| Anmerkungen: |
Date Completed 10.12.2021 Date Revised 14.12.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202108304 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM332027716 |
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| 245 | 1 | 0 | |a Nitrene Photochemistry of Manganese N-Haloamides* |
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2021 Wiley-VCH GmbH. | ||
| 520 | |a Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C-H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1 H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C-H bonds, such as the α-C-H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C-H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn-N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N-I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 650 | 4 | |a C−H Amination | |
| 650 | 4 | |a Group Transfer Catalysis | |
| 650 | 4 | |a Metal Nitrenes | |
| 650 | 4 | |a Photochemistry | |
| 650 | 4 | |a Reactive Intermediates | |
| 700 | 1 | |a Reid, Kaleb A |e verfasserin |4 aut | |
| 700 | 1 | |a Hicks, Madeline H |e verfasserin |4 aut | |
| 700 | 1 | |a Das, Anuvab |e verfasserin |4 aut | |
| 700 | 1 | |a Figgins, Matthew T |e verfasserin |4 aut | |
| 700 | 1 | |a Bhuvanesh, Nattamai |e verfasserin |4 aut | |
| 700 | 1 | |a Ozarowski, Andrew |e verfasserin |4 aut | |
| 700 | 1 | |a Telser, Joshua |e verfasserin |4 aut | |
| 700 | 1 | |a Powers, David C |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1002/anie.202108304 |3 Volltext |
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