Diametrically opposite trends in alkene insertion in late and early transition metal compounds: Relevance to transition-metal-catalyzed polymerization of polar vinyl monomers

Myeongsoon Kang, Ayusman Sen, Lev Zakharov, Arnold L. Rheingold

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Variable-temperature 1H NMR studies of the reaction of cationic (α-diimine)Pd-alkyl complexes with alkenes are presented. The studies reveal that vinyl bromide coordinates to the Pd(II)-Me complex followed by migratory insertion and β-bromo elimination, to generate free propene. Propene further reacts to give β-agostic Pd(II)-tert-butyl species. From the reactions with vinyl bromide, stable chloro-bridged dicationic Pd complex was isolated and characterized. For a series of alkenes (CH2=CHX), the rate for migratory insertion decreases as follows: X = CO2Me > Br > H > Me.

Original languageEnglish (US)
Pages (from-to)12080-12081
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number41
DOIs
StatePublished - Oct 16 2002

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Transition metal compounds
Alkenes
Polymerization
Olefins
Propylene
Transition metals
Monomers
Metals
Nuclear magnetic resonance
Temperature
vinyl bromide
propylene
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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abstract = "Variable-temperature 1H NMR studies of the reaction of cationic (α-diimine)Pd-alkyl complexes with alkenes are presented. The studies reveal that vinyl bromide coordinates to the Pd(II)-Me complex followed by migratory insertion and β-bromo elimination, to generate free propene. Propene further reacts to give β-agostic Pd(II)-tert-butyl species. From the reactions with vinyl bromide, stable chloro-bridged dicationic Pd complex was isolated and characterized. For a series of alkenes (CH2=CHX), the rate for migratory insertion decreases as follows: X = CO2Me > Br > H > Me.",
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Diametrically opposite trends in alkene insertion in late and early transition metal compounds : Relevance to transition-metal-catalyzed polymerization of polar vinyl monomers. / Kang, Myeongsoon; Sen, Ayusman; Zakharov, Lev; Rheingold, Arnold L.

In: Journal of the American Chemical Society, Vol. 124, No. 41, 16.10.2002, p. 12080-12081.

Research output: Contribution to journalArticle

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AU - Rheingold, Arnold L.

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