Supramolecular Assembly Promotes the Electrocatalytic Reduction of Carbon Dioxide by Re(I) Bipyridine Catalysts at a Lower Overpotential

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• 作者：Charles W. Machan ; Steven A. Chabolla ; Jian Yin ; Michael K. Gilson ; F. Akif Tezcan ; Clifford P. Kubiak
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 15, 2014
• 年：2014
• 卷：136
• 期：41
• 页码：14598-14607
• 全文大小：508K
• ISSN：1520-5126

文摘

The addition of methyl acetamidomethyl groups at the 4,4鈥?positions of a 2,2鈥?bipyridyl ligand is found to enhance the rate of a bimolecular reduction mechanism of CO₂ by Re^I fac-tricarbonyl chloride complexes. Electrochemical studies, spectroelectrochemical measurements, and molecular dynamics simulations indicate that these methyl acetamidomethyl groups promote the formation of a hydrogen-bonded dimer. This supramolecular complex catalyzes the reductive disproportionation of CO₂ to CO and CO₃^{2鈥?/sup> at a lower overpotential (ca. 250 mV) than the corresponding single-site 2 e鈥?/sup> reduction of CO₂ to CO and H₂O catalyzed by the corresponding model complex with a 4,4鈥?dimethyl-2,2鈥?bipyridyl ligand. These findings demonstrate that noncovalent self-assembly can modulate the catalytic properties of metal complexes by favoring alternate catalytic pathways.}