A phosphine-accelerated ArF-chloride bond activation process by palladium

Meital Orbach, Olena V. Zenkina, Yael Diskin-Posner, Mark A. Iron, Milko van der Boom

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We present a mechanistic study demonstrating selective Arf-Cl bond activation preceded by η2 coordination of Pd(PEt 3)2 to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Arf-Cl bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt3. The latter pathway is significantly enhanced, since PEt 3 promotes dissociation of Pd(PEt3)3 from the C=C moiety followed by activation of the Arf-Cl bond. Our observations also show that PEt3 can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF- PBE+dv2/SDD(d) level of theory).

Original languageEnglish
Pages (from-to)3074-3082
Number of pages9
JournalOrganometallics
Volume32
Issue number10
DOIs
Publication statusPublished - May 24 2013

Fingerprint

phosphine
Palladium
phosphines
Chlorides
palladium
Chemical activation
chlorides
activation
reaction control
deuterium fluorides
walking
Surface mount technology
Toluene
Density functional theory
toluene
selectivity
dissociation
density functional theory
rings
Substrates

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

A phosphine-accelerated ArF-chloride bond activation process by palladium. / Orbach, Meital; Zenkina, Olena V.; Diskin-Posner, Yael; Iron, Mark A.; van der Boom, Milko.

In: Organometallics, Vol. 32, No. 10, 24.05.2013, p. 3074-3082.

Research output: Contribution to journalArticle

Orbach, M, Zenkina, OV, Diskin-Posner, Y, Iron, MA & van der Boom, M 2013, 'A phosphine-accelerated ArF-chloride bond activation process by palladium', Organometallics, vol. 32, no. 10, pp. 3074-3082. https://doi.org/10.1021/om400295p
Orbach, Meital ; Zenkina, Olena V. ; Diskin-Posner, Yael ; Iron, Mark A. ; van der Boom, Milko. / A phosphine-accelerated ArF-chloride bond activation process by palladium. In: Organometallics. 2013 ; Vol. 32, No. 10. pp. 3074-3082.
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