Retro-Brook rearrangement induces the formation of an octahedral nickel(benzamidinate) complex; Synthesis, structure and catalytic activity

Elza Nelkenbaum, Moshe Kapon, Moris S. Eisen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

The neutral octahedral nickel complex (PhC(NSiMe3)NC(Ph) CHSiMe3)Ni(acac)(TMEDA) (7), has been synthesized and characterized including X-ray diffraction analysis. The complex was formed by the reaction of Ni(acac)2(TMEDA) with the lithium salt of the corresponding β-diketiminate ligand. The formation of the benzamidinate motif from the corresponding β-diketiminate is a consequence of a retro-Brook isomerization that is operative only at the nickel centre. A plausible mechanism for the metal mediated isomerization is proposed. When complex 7 was activated with MAO it showed a good catalytic activity for the addition polymerization of norbornene. Furthermore, this catalytic system has been found to oligomerize ethylene to a mixture of butenes and hexenes with a high turnover frequency, η = 29,300 h-1, when the reaction is performed in dichloromethane.

Original languageEnglish
Pages (from-to)2297-2305
Number of pages9
JournalJournal of Organometallic Chemistry
Volume690
Issue number9
DOIs
StatePublished - 29 Apr 2005
Externally publishedYes

Keywords

  • Diketiminates
  • Ethylene oligomerization
  • Nickel
  • Polymerization
  • Retro brook isomerization
  • X-ray structure

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