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Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Paper ID Volume ID Publish Year Pages File Format Full-Text
54296 47004 2014 9 PDF Available
Title
Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties
Abstract

•A new rhenium bipyridine complex with ancillary BODIPY units ([Re(BB2)(CO)3Cl]) was prepared and the structure was determined.•[Re(BB2)(CO)3Cl] supports an intriguing redox chemistry and can store multiple electrons.•[Re(BB2)(CO)3Cl] displays a higher TOF for reduction of CO2 to CO versus similar rhenium complexes.•[Re(BB2)(CO)3Cl] supports an unusual photochemistry that is of interest to the photocatalytic reduction of CO2.

The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO)3Cl] can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions – two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO)3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M−1 s−1 at an applied potential of −2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO2 reduction and are distinct from those that are typically observed for fac-ReI(CO)3 complexes.

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Keywords
BODIPY; Carbon dioxide; Catalysis; Electrochemistry; Photochemistry; Rhenium bipyridine derivatives
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Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Today - Volume 225, 15 April 2014, Pages 149–157
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us