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Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids. | LitMetric

Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids.

J Am Chem Soc

Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, D-33615 Bielefeld, Germany.

Published: December 2024

AI Article Synopsis

  • The study investigates the activation and functionalization of carbon dioxide using stable Group 14 diradicals, specifically focusing on anionic dicarbene frameworks.
  • These diradicaloids react with CO to form various compounds through cycloaddition, with behaviors varying significantly depending on the element (Si, Ge, Sn) present in the diradical structure.
  • The research includes detailed molecular analysis through X-ray diffraction and theoretical insights from DFT calculations to understand the mechanisms involved in the formation of these compounds.

Article Abstract

Although diradicals should exhibit a rather small reaction barrier as compared to closed-shell species for activating kinetically inert molecules, the activation and functionalization of carbon dioxide with stable main-group diradicals remain virtually unexplored. In this work, we present a thorough study on CO activation, reversible capture, and (de)oxygenation mediated by stable Group 14 singlet diradicals (i.e., diradicaloids) [(ADC)E] (E = Si, Ge, Sn) based on an anionic dicarbene (ADC) framework (ADC = PhC{N(Dipp)C}; Dipp = 2,6-PrCH). [(ADC)E] readily undergo [4 + 2]-cycloadditions with CO to result in barrelene-type bis-metallylenes [(ADC)E](OC═O). The CO addition is reversible for E = Ge; thus, CO detaches under vacuum or at an elevated temperature and regenerates [(ADC)Ge]. [(ADC)Sn](OC═O) is isolable but deoxygenates additional CO to form [(ADC)Sn](OCO) and CO. [(ADC)Si](OC═O) is extremely reactive and could not be isolated or detected as it spontaneously reacts further with CO to yield elusive monomeric Si(IV) oxides [(ADC)Si(O)](CO) or carbonates [(ADC)Si(CO)](CO) ( = 1 or 2) via the (de)oxygenation of CO. The molecular structures of all isolated compounds have been established by X-ray diffraction, and a mechanistic insight of their formation has been suggested by DFT calculations.

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Source
http://dx.doi.org/10.1021/jacs.4c15062DOI Listing

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