Solvent-Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products

Michael C Thompson; Jacob Ramsay; J Mathias Weber

doi:10.1002/anie.201607445

Solvent-Driven Reductive Activation of CO₂ by Bismuth: Switching from Metalloformate Complexes to Oxalate Products

Angew Chem Int Ed Engl. 2016 Nov 21;55(48):15171-15174. doi: 10.1002/anie.201607445. Epub 2016 Oct 12.

Authors

Michael C Thompson¹, Jacob Ramsay¹, J Mathias Weber¹

Affiliation

¹ JILA and Department of Chemistry and Biochemistry, University of Colorado, 440 UCB, Boulder, CO, 80309-0440, USA.

PMID: 27730755
DOI: 10.1002/anie.201607445

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.

Keywords: IR spectroscopy; bismuth; cluster compounds; heterogeneous catalysis; solvation.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.