Carbon dioxide interaction with metal atoms: Matrix isolation spectroscopic study and DFT calculations

J. Mascetti, F. Galan, I. Papai

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This paper collects the results obtained in different studies on the interaction of the CO2 molecule with transition metal atoms, using matrix isolation FTIR spectroscopy and density functional theory (DFT). Late-transition metal atoms (Fe, Co, Ni and Cu) form one-to-one M(CO2) complexes, while those from the left-hand side in the periodic table (Ti, V, and Cr) insert spontaneously into a CO bond yielding oxocarbonyl species. Owing to isotopic experiments with 13CO2 and C18O2, these results allow spectroscopic identification of carbon dioxide bonding modes in organometallic species containing CO2 moiety. Special attention is paid to the interaction of CO2 molecule with Ni and Ti atoms. In neat CO2 matrices, it is shown that CO2 is side-on coordinated to nickel in a 1:1 complex. The binding energy is weak (18 kcal mol-1). In argon diluted matrices, no reaction occurs, even after annealing. Interestingly, the coordination of CO2 is promoted by adding N2 in the rare gas matrix. This is rationalized by comparing the potential energy curves corresponding to the interaction of the Ni atom or the NiN2 moiety with CO2. The binding energy is then 32 kcal mol -1. DFT calculations show that Ti inserts with no energy barrier into a CO bond, resulting in an OTiCO insertion product, which is far more stable than any of the possible Ti(CO2) complexes and reactive towards CO2. An intrinsic reaction path for the insertion process is investigated. (C) 1999 Elsevier Science S.A.

Original languageEnglish
Pages (from-to)557-576
Number of pages20
JournalCoordination Chemistry Reviews
Publication statusPublished - Dec 1 1999


  • Carbon dioxide
  • Coordination complexes
  • DFT calculations
  • FTIR spectroscopy
  • Matrix isolation
  • Transition metal atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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