A Proton Directly Attacks 1,5-Cyclooctadiene in Bis(1,5-cyclooctadiene)nickel(0) in the Formation of a Keim Type Oligomerization Catalyst

Full proton and carbon assignments have been obtained for ((1,4,5-η)-cyclooctenyl)(1,1,1,5,5,5-hexafluoro-2,4-pentadionato)nickel(II) (1), a Keim type ethylene oligomerization catalyst, which is afforded by treatment of bis(1,5-cyclooctadiene)nickel with 1,1,1,5,5,5-hexafluoroacetylacetone. The larg...

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Veröffentlicht in:Organometallics 1998-11, Vol.17 (24), p.5367-5373
Hauptverfasser: Åkermark, Björn, Martin, Jeff, Nyström, Jan-Erik, Strömberg, Staffan, Svensson, Mats, Zetterberg, Krister, Zuber, Marek
Format: Artikel
Sprache:eng
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Zusammenfassung:Full proton and carbon assignments have been obtained for ((1,4,5-η)-cyclooctenyl)(1,1,1,5,5,5-hexafluoro-2,4-pentadionato)nickel(II) (1), a Keim type ethylene oligomerization catalyst, which is afforded by treatment of bis(1,5-cyclooctadiene)nickel with 1,1,1,5,5,5-hexafluoroacetylacetone. The larger metallacycle formed by nickel and the (1,4,5-η)-cyclooctenyl ligand in 1 is shown to be in a “nickela chair” conformation. The reaction of bis(1,5-cyclooctadiene)nickel with 1,1,1,5,5,5-hexafluoroacetylacetone-d 2 at low temperature shows a 70% incorporation of a deuterium atom anti to nickel at a β-carbon. This observation is incompatible with a hydride migration path for the formation of 1 but fully consistent with a direct protonation of an alkene coordinated to an electron-donating nickel.
ISSN:0276-7333
1520-6041
DOI:10.1021/om971119s