Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
67036 | Journal of Molecular Catalysis A: Chemical | 2010 | 8 Pages |
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.
Graphical abstractA fundamental possibility is shown for the formation of the cationic nickel(I) complexes stabilized in solution by olefin ligands.Figure optionsDownload full-size imageDownload as PowerPoint slide