Molecular Rubies in Photoredox Catalysis
The molecular ruby [Cr(tpe)2]3+ and the tris(bipyridine) chromium(III) complex [Cr(dmcbpy)3]3+ as well as the tris(bipyrazine)ruthenium(II) complex [Ru(bpz)3]2+ were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4′-dimethoxyc...
| Hoofdauteurs: | , , |
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| Formaat: | Artikel |
| Taal: | English |
| Gepubliceerd in: |
Frontiers Media S.A.
2022-04-01
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| Reeks: | Frontiers in Chemistry |
| Onderwerpen: | |
| Online toegang: | https://www.frontiersin.org/articles/10.3389/fchem.2022.887439/full |
| _version_ | 1830459488051658752 |
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| author | Steven Sittel Robert Naumann Katja Heinze |
| author_facet | Steven Sittel Robert Naumann Katja Heinze |
| author_sort | Steven Sittel |
| collection | DOAJ |
| description | The molecular ruby [Cr(tpe)2]3+ and the tris(bipyridine) chromium(III) complex [Cr(dmcbpy)3]3+ as well as the tris(bipyrazine)ruthenium(II) complex [Ru(bpz)3]2+ were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4′-dimethoxycarbonyl-2,2′-bipyridine, bpz = 2,2′-bipyrazine), while [Cr(ddpd)2]3+ serves as a control system (ddpd = N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the CrIII driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst [Cr(tpe)2]3+ outcompetes [Cr(dmcbpy)3]3+ and even [Ru(bpz)3]2+ in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of [Cr(tpe)2]3+ in this photoredox catalytic system. |
| first_indexed | 2024-12-21T10:56:42Z |
| format | Article |
| id | doaj.art-9042b4be53d44e4b828fe7d9ff75195b |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-12-21T10:56:42Z |
| publishDate | 2022-04-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-9042b4be53d44e4b828fe7d9ff75195b2022-12-21T19:06:30ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462022-04-011010.3389/fchem.2022.887439887439Molecular Rubies in Photoredox CatalysisSteven SittelRobert NaumannKatja HeinzeThe molecular ruby [Cr(tpe)2]3+ and the tris(bipyridine) chromium(III) complex [Cr(dmcbpy)3]3+ as well as the tris(bipyrazine)ruthenium(II) complex [Ru(bpz)3]2+ were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4′-dimethoxycarbonyl-2,2′-bipyridine, bpz = 2,2′-bipyrazine), while [Cr(ddpd)2]3+ serves as a control system (ddpd = N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the CrIII driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst [Cr(tpe)2]3+ outcompetes [Cr(dmcbpy)3]3+ and even [Ru(bpz)3]2+ in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of [Cr(tpe)2]3+ in this photoredox catalytic system.https://www.frontiersin.org/articles/10.3389/fchem.2022.887439/fullchromiumradical cationDiels-Alder reaction[4+2] cycloadditionphotoredox catalysissinglet oxygen |
| spellingShingle | Steven Sittel Robert Naumann Katja Heinze Molecular Rubies in Photoredox Catalysis Frontiers in Chemistry chromium radical cation Diels-Alder reaction [4+2] cycloaddition photoredox catalysis singlet oxygen |
| title | Molecular Rubies in Photoredox Catalysis |
| title_full | Molecular Rubies in Photoredox Catalysis |
| title_fullStr | Molecular Rubies in Photoredox Catalysis |
| title_full_unstemmed | Molecular Rubies in Photoredox Catalysis |
| title_short | Molecular Rubies in Photoredox Catalysis |
| title_sort | molecular rubies in photoredox catalysis |
| topic | chromium radical cation Diels-Alder reaction [4+2] cycloaddition photoredox catalysis singlet oxygen |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2022.887439/full |
| work_keys_str_mv | AT stevensittel molecularrubiesinphotoredoxcatalysis AT robertnaumann molecularrubiesinphotoredoxcatalysis AT katjaheinze molecularrubiesinphotoredoxcatalysis |