• V. V. Saraev
  • P. B. Kraikivskii
  • D. A. Matveev
  • V. V. Bocharova
  • S. K. Petrovskii
  • S. N. Zelinskii
  • A. I. Vilms
  • Hans Friedrich Klein

The catalytic system Ni(COD)2/BF3·OEt2 has been studied in conversions of 1,5-cyclooctadiene under argon and ethylene atmosphere. It has been demonstrated that the catalytic system formed under argon exhibits a high effectiveness in cycloisomerization of 1,5-COD surpassing in this characteristic all known nickel complex catalysts (selectivity to bicyclo-[3.3.0]-octene-2 is up to 99.5% at 100% conversion). In the case of ethylene atmosphere the system produces mainly dimers (yield of cyclodimers above 70%). It has been shown that the catalytic system Ni(COD)2/BF3·OEt2 has the feature of "a living catalyst" consisting in resuming the initial activity with a new portion of 1,5-COD added when the monomer was fully exhausted. The main and side products of the 1,5-COD conversion have been identified with GC-MS and preparative liquid chromatography combined with NMR and IR spectroscopy. Based on EPR and IR spectroscopic data a mechanism for the catalytic performance of the Ni(COD)2/BF3·OEt2 system in argon or ethylene atmospheres is suggested. It has been shown that Ni(0) is oxidized by the Lewis acid to Ni(I) which is stabilized by substrate molecules in a mononuclear form without involvement of conventional organoelement entities. Three sorts of paramagnetic nickel species have been found: ionic complexes containing π-coordinated COD ligands; ionic complexes σ-bonded to COD; complexes as intimate pairs with BF4- counter ions. A mechanism for the catalytic conversion of 1,5-cyclooctadiene is proposed.

Original languageEnglish
Pages (from-to)231-238
Number of pages8
JournalJournal of Molecular Catalysis A: Chemical
Volume315
Issue number2
DOIs
StatePublished - 15 Jan 2010

    Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

    Research areas

  • 1,5-Cyclooctadiene, Cyclodimerization, Cycloisomerization, Mechanism, Nickel(I)

ID: 51891745