期刊
INORGANIC CHEMISTRY
卷 60, 期 22, 页码 16953-16965出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c01609
关键词
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资金
- U.S. Department of Energy, Office of Science, Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences [DE-SC0012704]
By electrochemically activating an organometallic Ruthenium(II) complex in acetonitrile solutions, the movement of protons from weak Brønsted acids to carbon dioxide (CO2) was coupled with the generation of a metal-hydride complex and a carbonate species, providing key intermediates for CO2 and proton reduction catalysis. These pathways may offer alternative approaches in electrosynthesis of chemical commodities through alkylation and carboxylation reactions.
The mechanistic identification of Nature's use of concerted reactions, in which all bond breaking and bond making occurs in a single step, has inspired rational designs for artificial synthetic transformations via pathways that bypass high-energy intermediates that would otherwise be thermodynamically and kinetically inaccessible. In this contribution we electrochemically activate an organometallic Ruthenium(II) complex to show that, in acetonitrile solutions, the movement of protons from weak Bronsted acids, such as water and methanol, is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO2)-a process termed proton-coupled group transfer-to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic acids, while their applicability to carbon acids may provide alternative approaches in the electrosynthesis of chemical commodities via alkylation and carboxylation reactions.
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