title: Solvent-Driven Reductive Activation of CO2by Bismuth: Switching from Metalloformate Complexes to Oxalate Products.
abstract: In this work, we investigated how the reductive activation of CO2with 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 CO2binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO-. Solvation with additional CO2molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, 440 UCB, Boulder, CO, 80309-0440, USA.
authors.forename: Michael C
authors.initials: MC
authors.lastname: Thompson
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, 440 UCB, Boulder, CO, 80309-0440, USA.
authors.forename: Jacob
authors.initials: J
authors.lastname: Ramsay
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, 440 UCB, Boulder, CO, 80309-0440, USA.
authors.forename: J Mathias
authors.identifier: 0000-0002-5493-5886
authors.initials: JM
authors.lastname: Weber
keywords: IR spectroscopy; bismuth; cluster compounds; heterogeneous catalysis; solvation