Premium
Solvent‐Driven Reductive Activation of CO 2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products
Author(s) -
Thompson Michael C.,
Ramsay Jacob,
Weber J. Mathias
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201607445
Subject(s) - bismuth , chemistry , solvation , oxalate , cluster (spacecraft) , ion , inorganic chemistry , photodissociation , density functional theory , molecule , catalysis , atom (system on chip) , photochemistry , computational chemistry , organic chemistry , computer science , embedded system , programming language
In this work, we investigated how the reductive activation of CO 2 with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass‐selected [Bi(CO 2 ) 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 CO 2 binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO − . Solvation with additional CO 2 molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.