Solvent-Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products.
Angew Chem Int Ed Engl
; 55(48): 15171-15174, 2016 11 21.
Article
em En
| MEDLINE
| ID: mdl-27730755
ABSTRACT
In this work, we investigated how the reductive activation of CO2 with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass-selected [Bi(CO2 )n ]- cluster ions was used to follow the structural evolution of the core ion with increasing cluster size. We interpreted the IR spectra by comparison with density-functional-theory calculations. The results show that CO2 binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO- . Solvation with additional CO2 molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.
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MEDLINE
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En
Ano de publicação:
2016
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Article