Vanadium insertion into CO2, CS2 and OCS: A comparative theoretical study

Imre Pápai, Yacine Hannachi, Sylvain Gwizdala, Joëlle Mascetti

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The reactions of the ground-state V(s2d3) atom with CO2, CS2, and OCS molecules have been studied at the B3LYP level of density functional theory in order to compare the insertion process for these three isovalent molecules. The relative stabilities of the adduct and insertion forms are calculated. The reaction barrier between these two forms are estimated for each system from the 4A″ and 4A′ potential energy curves defined in terms of the C-X (X=O,S) intrinsic reaction coordinate. The barrier to metal insertion from the side-on structure is rather low (ca 4 kcal/mol) for CO2 and CS2, however, whereas V(CO2) is well above the OVCO insertion product, the V(CS2) complex is only 4.2 less stable than SVCS. Consequently, coordination of CS2 to metal centers is stronger than that of CO2. Our calculations indicate no energy barrier for the insertion of V in the CS bond of OCS, whereas the insertion in the CO bond is less favored than in CO2. We show that each insertion reaction proceeds on a single potential energy surface. Differences in the energetics of the three reactions are related to the molecular properties of CO2, CS2, and OCS.

Original languageEnglish
Pages (from-to)4181-4186
Number of pages6
JournalJournal of Physical Chemistry A
Issue number16
Publication statusPublished - Apr 25 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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