A dinuclear rhenium complex in the electrochemically driven homogeneous and heterogeneous H⁺/CO₂-reduction

Abstract

Herein, we report on the homogeneous and heterogeneous H+/CO2-reduction forming syngas with a binuclear Re complex having a proton rely.

Manganese and Rhenium Tricarbonyl Complexes Equipped with Proton Relays in the Electrochemical CO2 Reduction Reaction

“…Molecular Re(CO) 3 complexes, which were anchored on carbon electrodes for heterogeneous CO 2 ‐reduction. [ 68,69 ] …”

“…We utilised the binuclear compound 50 modified with a pyrene group in the ligand backbone in the electrochemical CO 2 catalysis. [ 69 ] Surprisingly, the complex modification led to a loss of selectivity under catalytic conditions in dmf/water solution. It produces CO and H 2 in about equal amounts in contrast to 24 , which was selective for CO formation under otherwise identical conditions.…”

Electrochemical CO2 Reduction Catalyzed by Binuclear LRe2(CO)6Cl2 and LMn2(CO)6Br2 Complexes with an Internal Proton Source

“…35 Encouraged by these results, we introduced the pyrene group in the backbone of 14 (18, Figure 2). 36 This modification leads to an additional reduction process at −2.70 V, which was assigned to the reduction of pyrene. All other reduction processes in 18 appeared at very similar potentials as in 14, and the species, which are formed during electroreduction, were proposed to be the same.…”

Role of Bimetallic Interactions in the Enhancement of Catalytic CO2 Reduction by a Macrocyclic Cobalt Catalyst

“…The completion of the catalytic cycle was proposed to involve a second CO 2 molecule as an oxide acceptor, resulting in the overall formation of CO and CO 3 2– . Following these initial findings, a number of Re-based catalysts containing two metal centers bridged by a linker have been prepared ,− with the intent to explore multimetal catalysis. With some enhancements in catalytic current and anodic shifts in onset potentials for catalysis, the only bimetallic intermediate confidently identified was a Re–Re dimer of two singly reduced sites, which is typically not considered as an active species toward CO 2 reduction. ,, Similarly, a series of bimetallic Co complexes have been used for photosensitized CO 2 reduction catalysis and their high performance was attributed to the cooperative effect of two metal centers. ,,, Again, with rare exceptions, the catalytic intermediates or kinetics of elementary catalytic steps implicating the involvement of two metal centers in catalysis have not been positively identified.…”