Neutral and cationic vanadium(III) alkyl and allyl complexes with a cyclopentadienyl-amine ancillary ligand

GH Liu, DJ Beetstra, A Meetsma, B Hessen*, Guohua Liu, Dirk J. Beetstra

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

36 Citations (Scopus)
286 Downloads (Pure)

Abstract

The (N,N-dimethylaminoethyl)cyclopentadienyI vanadium(III) complex [eta(5),eta(1)-C5H4(CH2)(2)-NMe2]VCl2(PMe3) (1), in which the pendant amine is coordinated to the metal center, was prepared by the reaction Of VCl3(PMe3)(2) with Li[C5H4(CH2)(2)NMe2] in THF. Reaction of 1 with 2 equiv of MeLi yields [eta(5)-C5H4(CH2)(2)NMe2]VMe2(PMe3)(2) (2), in which the amine is released in favor of the binding of a second phosphine. Compound 2 reacts with [PhNMe2H]-[BPh4] to form the ionic complex {[eta(5),eta(2)-C5H4(CH2)(2)N(Me)CH2]V(PMe3)(2)}[BPh4] (3), in which a methyl group of the pendant NMe2 functionality is metalated, and 2 equiv of methane. Reaction of 1 with allylmagnesium chloride yields [eta(5)-C5H4(CH2)(2)NMe2]V(eta(3)-C3H5)Cl(PMe3) (4), in which the amine is released in favor of the eta(3)-bonding of the allyl ligand. Methylation of 4 to yield thermally labile [eta(5)-C5H4(CH2)(2)NMe2]V(eta(3)-C3H5)Me(PMe3) (5), followed by reaction with [PhNMe2H] [BPh4], gives protonation exclusively at the methyl group to yield the ionic allyl complex {[eta(5),eta(1)-C5H4(CH2)(2)NMe2]V(eta(3)-C3H5)(PMe3)}[BPh4] (6) without concomitant NMe2 metalation.

Original languageEnglish
Pages (from-to)3914-3920
Number of pages7
JournalOrganometallics
Volume23
Issue number16
DOIs
Publication statusPublished - 2-Aug-2004

Keywords

  • OLEFIN POLYMERIZATION
  • ETHYLENE POLYMERIZATION
  • (ARYLIMIDO)(ARYLOXO)VANADIUM(V) COMPLEXES
  • BOROHYDRIDE COMPOUNDS
  • ZIEGLER-NATTA
  • SIDE-CHAIN
  • REACTIVITY
  • BEHAVIOR
  • CATALYST
  • COPOLYMERIZATION

Cite this