title: Rhenium Complexes Based on 2-Pyridyl-1,2,3-triazole Ligands: A New Class of CO2Reduction Catalysts.
abstract: A series of [Re(N^N)(CO)3(X)] (N^N = diimine and X = halide) complexes based on 4-(2-pyridyl)-1,2,3-triazole (pyta) and 1-(2-pyridyl)-1,2,3-triazole (tapy) diimine ligands have been prepared and electrochemically characterized. The first ligand-based reduction process is shown to be highly sensitive to the nature of the isomer as well as to the substituents on the pyridyl ring, with the peak potential changing by up to 700 mV. The abilities of this class of complexes to catalyze the electroreduction and photoreduction of CO2were assessed for the first time. It is found that only Re pyta complexes that have a first reduction wave with a peak potential at ca. -1.7 V vs SCE are active, producing CO as the major product, together with small amounts of H2and formic acid. The catalytic wave that is observed in the CVs is enhanced by the addition of water or trifluoroethanol as a proton source. Long-term controlled potential electrolysis experiments gave total Faradaic yield close to 100%. In particular, functionalization of the triazolyl ring with a 2,4,6-tri-tert-butylphenyl group provided the catalyst with a remarkable stability.
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, PSL Research University, Collège de France, CNRS UMR8229, Université Pierre et Marie Curie , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.|Département de Chimie, Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, Ecole Normale Supérieure, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Chimie ParisTech, PSL Research University, Unité de Technologies Chimiques et Biologiques pour la Santé , F-75005 Paris, France.|CNRS, UTCBS UMR 8258 , F-75006 Paris, France.|Université Paris Descartes, Sorbonne-Paris-Cité, UTCBS , F-75006 Paris, France.|INSERM, UTCBS U 1022 , F-75006 Paris, France.
authors.forename: H Y Vincent
authors.initials: HY
authors.lastname: Ching
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, PSL Research University, Collège de France, CNRS UMR8229, Université Pierre et Marie Curie , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Xia
authors.initials: X
authors.lastname: Wang
authors.affiliation: Département de Chimie, Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, Ecole Normale Supérieure, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Menglan
authors.initials: M
authors.lastname: He
authors.affiliation: Département de Chimie, Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, Ecole Normale Supérieure, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Noemi
authors.initials: N
authors.lastname: Perujo Holland
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, Université Paris-Sud, UMR CNRS 8182, Université Paris-Saclay , 91405 Orsay, France.
authors.forename: Régis
authors.initials: R
authors.lastname: Guillot
authors.affiliation: Chimie ParisTech, PSL Research University, Unité de Technologies Chimiques et Biologiques pour la Santé , F-75005 Paris, France.|CNRS, UTCBS UMR 8258 , F-75006 Paris, France.|Université Paris Descartes, Sorbonne-Paris-Cité, UTCBS , F-75006 Paris, France.|INSERM, UTCBS U 1022 , F-75006 Paris, France.
authors.forename: Cyrine
authors.initials: C
authors.lastname: Slim
authors.affiliation: Chimie ParisTech, PSL Research University, Unité de Technologies Chimiques et Biologiques pour la Santé , F-75005 Paris, France.|CNRS, UTCBS UMR 8258 , F-75006 Paris, France.|Université Paris Descartes, Sorbonne-Paris-Cité, UTCBS , F-75006 Paris, France.|INSERM, UTCBS U 1022 , F-75006 Paris, France.
authors.forename: Sophie
authors.initials: S
authors.lastname: Griveau
authors.affiliation: Département de Chimie, Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, Ecole Normale Supérieure, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Hélène C
authors.initials: HC
authors.lastname: Bertrand
authors.affiliation: Département de Chimie, Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, Ecole Normale Supérieure, CNRS, Laboratoire des Biomolécules , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Clotilde
authors.identifier: http://orcid.org/0000-0003-0255-1650
authors.initials: C
authors.lastname: Policar
authors.affiliation: Chimie ParisTech, PSL Research University, Unité de Technologies Chimiques et Biologiques pour la Santé , F-75005 Paris, France.|CNRS, UTCBS UMR 8258 , F-75006 Paris, France.|Université Paris Descartes, Sorbonne-Paris-Cité, UTCBS , F-75006 Paris, France.|INSERM, UTCBS U 1022 , F-75006 Paris, France.
authors.forename: Fethi
authors.initials: F
authors.lastname: Bedioui
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, PSL Research University, Collège de France, CNRS UMR8229, Université Pierre et Marie Curie , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Marc
authors.identifier: http://orcid.org/0000-0002-8016-4747
authors.initials: M
authors.lastname: Fontecave