Open AccessRevisiting Reduction of CO2 to Oxalate with First-Row Transition Metals: Irreproducibility, Ambiguous Analysis, and Conflicting Reactivity
Author(s) -
Maximilian Marx,
Holm Frauendorf,
Anke Spannenberg,
Helfried Neumann,
Matthias Beller
Publication year - 2022
Publication title -
jacs au
Language(s) - English
Resource type - Journals
ISSN - 2691-3704
DOI - 10.1021/jacsau.2c00005
Subject(s) - oxalate , reactivity (psychology) , catalysis , chemistry , transition metal , reduction (mathematics) , redox , reductive elimination , carbon dioxide , work (physics) , combinatorial chemistry , computer science , inorganic chemistry , organic chemistry , thermodynamics , mathematics , physics , medicine , alternative medicine , geometry , pathology
Construction of higher C ≥2 compounds from CO 2 constitutes an attractive transformation inspired by nature's strategy to build carbohydrates. However, controlled C-C bond formation from carbon dioxide using environmentally benign reductants remains a major challenge. In this respect, reductive dimerization of CO 2 to oxalate represents an important model reaction enabling investigations on the mechanism of this simplest CO 2 coupling reaction. Herein, we present common pitfalls encountered in CO 2 reduction, especially its reductive coupling, based on established protocols for the conversion of CO 2 into oxalate. Moreover, we provide an example to systematically assess these reactions. Based on our work, we highlight the importance of utilizing suitable orthogonal analytical methods and raise awareness of oxidative reactions that can likewise result in the formation of oxalate without incorporation of CO 2 . These results allow for the determination of key parameters, which can be used for tailoring of prospective catalytic systems and will promote the advancement of the entire field.