Ethylene addition to Ru({double bond, long}CH2)({double bond, long}O)3 - A theoretical study

Robin Haunschild, Sandor Tüllmann, Gernot Frenking, Max C. Holthausen

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Abstract

Quantum chemical calculations using density functional theory (B3LYP) were carried out to elucidate the reaction pathways for ethylene addition to the ruthenium compound RuO3CH2. These investigations show that the parent compound is relatively unstable and its rearrangement gives access to very diverse isomers and addition products with comparable relative energies and reaction barriers. The results are compared to our previous study on the analogous osmium system OsO3CH2 and we show that reactivity of both compounds towards ethylene is quite similar. In both cases, the [3 + 2]C,O cycloaddition pathway is preferred kinetically and thermodynamically. The exothermicity (-68.8 kcal/mol) of this reaction is higher for the ruthenium system than for the osmium homologue. While this pathway is unrivaled for the osmium system, the [3 + 2]O,O cycloaddition pathway is able to compete kinetically for the ruthenium system.

Original languageEnglish
Pages (from-to)1081-1090
Number of pages10
JournalJournal of Organometallic Chemistry
Volume694
Issue number7-8
DOIs
StatePublished - 1 Apr 2009
Externally publishedYes

Keywords

  • Carbenes
  • Oxidation reactions
  • Quantum chemical calculations
  • Reaction mechanisms
  • Ruthenium compounds

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