RT Journal Article
T1 Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids
A1 Ebeler, F.
A1 Neuman, B.
A1 Stammler, H.-G.
A1 Fernández López, Israel
A1 Ghadwal, R. S.
AB 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 CO2 activation, reversible capture, and (de)oxygenation mediated by stable Group 14 singlet diradicals (i.e., diradicaloids) [(ADC)E]2 (E = Si, Ge, Sn) based on an anionic dicarbene (ADC) framework (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3). [(ADC)E]2 readily undergo [4 + 2]-cycloadditions with CO2 to result in barrelene-type bis-metallylenes [(ADC)E]2(OC═O). The CO2 addition is reversible for E = Ge; thus, CO2 detaches under vacuum or at an elevated temperature and regenerates [(ADC)Ge]2. [(ADC)Sn]2(OC═O) is isolable but deoxygenates additional CO2 to form [(ADC)Sn]2(O2CO) and CO. [(ADC)Si]2(OC═O) is extremely reactive and could not be isolated or detected as it spontaneously reacts further with CO2 to yield elusive monomeric Si(IV) oxides [(ADC)Si(O)]2(COn) or carbonates [(ADC)Si(CO3)]2(COn) (n = 1 or 2) via the (de)oxygenation of CO2. 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.
PB ACS
YR 2024
FD 2024-12-08
LK https://hdl.handle.net/20.500.14352/114716
UL https://hdl.handle.net/20.500.14352/114716
LA eng
NO Ebeler, Falk, et al. «Structural Snapshots of Reversible Carbon Dioxide Capture and (De)Oxygenation at Group 14 Diradicaloids». Journal of the American Chemical Society, vol. 146, n.o 50, diciembre de 2024, pp. 34979-89.
DS Docta Complutense
RD 15 dic 2025