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CO2 to CO: Photo‐ and electrocatalytic conversion based on Re(I) Bis‐Arene Frameworks: synergisms between catalytic subunits


Hernández‐Valdés, Daniel; Fernández‐Terán, Ricardo; Probst, Benjamin; Spingler, Bernhard; Alberto, Roger (2020). CO2 to CO: Photo‐ and electrocatalytic conversion based on Re(I) Bis‐Arene Frameworks: synergisms between catalytic subunits. Helvetica Chimica Acta, 103(10):online.

Abstract

Reduction of CO2 to CO and H2O is a two electron/two proton process. For this process, multinuclear complexes offer advantages by concentrating reduction equivalents more efficiently than mononuclear systems. We present novel complexes with [Re(η6‐C6H6)2]+ as scaffold conjugated to one or two catalytically active [Ru(dmbpy)(CO)2Cl2] subunits (dmbpy=5,5′‐dimethyl‐2,2′‐bipyridine). The [Re(η6‐C6H6)2]+ scaffold was chosen due to its very high photo‐ and chemical stability, as well as the multiple degrees of freedom it offers for any conjugated functionalities. High efficiency and selectivity for the reduction of CO2 to CO (over H2 or HCOOH) is reported. TONs and TOFs were found to be comparable or higher than for the catalyst subunit without the rhenium framework. Cooperativity in photo‐ and electrocatalysis is observed for the complex comprising two catalytic subunits. The synergistic communication between the two catalytic subunits is responsible for the observed enhancement in both photo‐ and electrocatalytic performance. Confirmation of electronic communication between the two [Ru(dmbpy)(CO)2Cl2] subunits as well as the elucidation of a possible mechanism was supported by electrochemistry, IR‐spectroelectrochemistry and DFT studies.

Abstract

Reduction of CO2 to CO and H2O is a two electron/two proton process. For this process, multinuclear complexes offer advantages by concentrating reduction equivalents more efficiently than mononuclear systems. We present novel complexes with [Re(η6‐C6H6)2]+ as scaffold conjugated to one or two catalytically active [Ru(dmbpy)(CO)2Cl2] subunits (dmbpy=5,5′‐dimethyl‐2,2′‐bipyridine). The [Re(η6‐C6H6)2]+ scaffold was chosen due to its very high photo‐ and chemical stability, as well as the multiple degrees of freedom it offers for any conjugated functionalities. High efficiency and selectivity for the reduction of CO2 to CO (over H2 or HCOOH) is reported. TONs and TOFs were found to be comparable or higher than for the catalyst subunit without the rhenium framework. Cooperativity in photo‐ and electrocatalysis is observed for the complex comprising two catalytic subunits. The synergistic communication between the two catalytic subunits is responsible for the observed enhancement in both photo‐ and electrocatalytic performance. Confirmation of electronic communication between the two [Ru(dmbpy)(CO)2Cl2] subunits as well as the elucidation of a possible mechanism was supported by electrochemistry, IR‐spectroelectrochemistry and DFT studies.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Life Sciences > Biochemistry
Life Sciences > Drug Discovery
Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Organic Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Biochemistry, Drug Discovery, Catalysis
Language:English
Date:1 October 2020
Deposited On:30 Oct 2020 16:28
Last Modified:31 Oct 2020 21:01
Publisher:Wiley Open Access
ISSN:1522-2675
OA Status:Green
Publisher DOI:https://doi.org/10.1002/hlca.202000147
Project Information:
  • : FunderSNSF
  • : Grant IDIZLSZ2_170856
  • : Project TitleSolar Light-driven Homogeneous Catalysis for Greener Industrial Processes with H2 as Energy Source and CO2 as C1 Building Block

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