Molecular Rubies in Photoredox Catalysis

Publication type:

Journal article

Metadata:

Autoren

Steven Sittel
Robert Naumann
Katja Heinze

Autoren-URL

https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000807684600001&DestLinkType=FullRecord&DestApp=WOS_CPL

DOI

10.3389/fchem.2022.887439

Externe Identifier

Clarivate Analytics Document Solution ID: 1X8FO
PubMed Identifier: 35464204

ISSN

2296-2646

Zeitschrift

FRONTIERS IN CHEMISTRY

Schlüsselwörter

chromium
radical cation
Diels-Alder reaction
[4+2] cycloaddition
photoredox catalysis
singlet oxygen

Artikelnummer

ARTN 887439

Datum der Veröffentlichung

2022

Status

Published

Titel

Molecular Rubies in Photoredox Catalysis

Sub types

Article

Ausgabe der Zeitschrift

Data source: Web of Science (Lite)

Other metadata sources:

Abstract

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.

Autoren

Steven Sittel
Robert Naumann
Katja Heinze

DOI

10.3389/fchem.2022.887439

eISSN

2296-2646

Zeitschrift

Frontiers in Chemistry

Online publication date

2022

Status

Published online

Herausgeber

Frontiers Media SA

Herausgeber URL

http://dx.doi.org/10.3389/fchem.2022.887439

Datum der Datenerfassung

2022

Titel

Molecular Rubies in Photoredox Catalysis

Ausgabe der Zeitschrift

Data source: Crossref

Abstract

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.

Addresses

Department of Chemistry, Johannes Gutenberg University, Mainz, Germany.

Autoren

Steven Sittel
Robert Naumann
Katja Heinze

DOI

10.3389/fchem.2022.887439

eISSN

2296-2646

Externe Identifier

PubMed Identifier: 35464204
PubMed Central ID: PMC9021569

Funding acknowledgements

Deutsche Forschungsgemeinschaft: HE2778/10-2

Open access

true

ISSN

2296-2646

Zeitschrift

Frontiers in chemistry

Sprache

eng

Medium

Electronic-eCollection

Online publication date

2022

Open access status

Open Access

Paginierung

887439

Datum der Veröffentlichung

2022

Status

Published

Publisher licence

CC BY

Datum der Datenerfassung

2022

Titel

Molecular Rubies in Photoredox Catalysis.

Sub types

research-article
Journal Article

Ausgabe der Zeitschrift

Files

https://www.frontiersin.org/articles/10.3389/fchem.2022.887439/pdf https://europepmc.org/articles/PMC9021569?pdf=render

Data source: Europe PubMed Central

Abstract

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.

Date of acceptance

2022

Autoren

Steven Sittel
Robert Naumann
Katja Heinze

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/35464204

DOI

10.3389/fchem.2022.887439

Externe Identifier

PubMed Central ID: PMC9021569

ISSN

2296-2646

Zeitschrift

Front Chem

Schlüsselwörter

Diels-Alder reaction
[4+2] cycloaddition
chromium
photoredox catalysis
radical cation
singlet oxygen

Sprache

eng

Country

Switzerland

Paginierung

887439

PII

887439

Datum der Veröffentlichung

2022

Status

Published online

Titel

Molecular Rubies in Photoredox Catalysis.

Sub types

Journal Article

Ausgabe der Zeitschrift

Data source: PubMed

Author's licence

CC-BY

Autoren

Steven Sittel
Robert Naumann
Katja Heinze

Hosting institution

Universitätsbibliothek Mainz

Sammlungen

DFG-491381577-G

Resource version

Published version

DOI

10.3389/fchem.2022.887439

Funding acknowledgements

Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 491381577

File(s) embargoed

false

Open access

true

ISSN

2296-2646

Zeitschrift

Frontiers in chemistry

Schlüsselwörter

540 Chemie
540 Chemistry and allied sciences

Sprache

eng

Open access status

Open Access

Paginierung

887439

Datum der Veröffentlichung

2022

Public URL

https://openscience.ub.uni-mainz.de/handle/20.500.12030/8213

Herausgeber

Frontiers Media

Datum der Datenerfassung

2022

Datum, an dem der Datensatz öffentlich gemacht wurde

2022

Zugang

Public

Titel

Molecular rubies in photoredox catalysis

Ausgabe der Zeitschrift

Files

molecular_rubies_in_photoredo-20221028152436261.pdf molecular_rubies_in_photoredo-20221102113317036.PDF

Data source: OPENSCIENCE.UB

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Anorganische Chemie - nachhaltige Koordinations- und Photochemie

Molecular Rubies in Photoredox Catalysis

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