Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

Florian Schendzielorz; Markus Finger; Josh Abbenseth; Christian Würtele; Vera Krewald; Sven Schneider

doi:10.1002/anie.201812125

Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

Florian Schendzielorz, Markus Finger, Josh Abbenseth, Christian Würtele, Vera Krewald, Sven Schneider

Department of Chemistry

University of Goettingen

Research output: Contribution to journal › Article › peer-review

87 Citations (SciVal)

Abstract

Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N−N bond energy. Photochemical strategies that drive N₂ fixation are scarcely developed. Here, the synthesis of a dinuclear N₂-bridged complex is presented upon reduction of a rhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2 H⁺/2 e⁻ transfer of the pincer ligand. A three-step cycle is demonstrated for N₂ to nitrile fixation that relies on electrochemical reduction, photochemical N₂-splitting and thermal nitrogen transfer.

Original language	English
Pages (from-to)	830-834
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	3
Early online date	7 Dec 2018
DOIs	https://doi.org/10.1002/anie.201812125
Publication status	Published - 7 Jan 2019

Bibliographical note

Funding

This work was supported by the European Research Council (ERC Consolidator Grant Agreement 646747, grant holder S.Sch.). V.K. acknowledges a 50th Anniversary Prize Fellowship from the University of Bath and its Balena High Performance Computing (HPC) Service. The authors thank Dr. C. Volkmann for solving the crystal structure of complex 8.

Keywords

electrochemistry
nitrogen fixation
photochemistry
pincer ligands
rhenium

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201812125

Cite this

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title = "Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen",

abstract = "Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N−N bond energy. Photochemical strategies that drive N2 fixation are scarcely developed. Here, the synthesis of a dinuclear N2-bridged complex is presented upon reduction of a rhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2 H+/2 e− transfer of the pincer ligand. A three-step cycle is demonstrated for N2 to nitrile fixation that relies on electrochemical reduction, photochemical N2-splitting and thermal nitrogen transfer.",

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AU - Schendzielorz, Florian

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AU - Abbenseth, Josh

AU - Würtele, Christian

AU - Krewald, Vera

AU - Schneider, Sven

PY - 2019/1/7

Y1 - 2019/1/7

N2 - Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N−N bond energy. Photochemical strategies that drive N2 fixation are scarcely developed. Here, the synthesis of a dinuclear N2-bridged complex is presented upon reduction of a rhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2 H+/2 e− transfer of the pincer ligand. A three-step cycle is demonstrated for N2 to nitrile fixation that relies on electrochemical reduction, photochemical N2-splitting and thermal nitrogen transfer.

AB - Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N−N bond energy. Photochemical strategies that drive N2 fixation are scarcely developed. Here, the synthesis of a dinuclear N2-bridged complex is presented upon reduction of a rhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2 H+/2 e− transfer of the pincer ligand. A three-step cycle is demonstrated for N2 to nitrile fixation that relies on electrochemical reduction, photochemical N2-splitting and thermal nitrogen transfer.

KW - electrochemistry

KW - nitrogen fixation

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Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

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Fingerprint

Balena High Performance Computing (HPC) System

High Performance Computing (HPC) Facility

Cite this

Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

Balena High Performance Computing (HPC) System

High Performance Computing (HPC) Facility

Cite this