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Mechanisms in the reaction of palladium(II)–π-allyl complexes with aryl halides: evidence for NHC exchange between two palladium complexes

Normand, Adrien T., Nechaev, Mikhail. S. and Cavell, Kingsley John 2009. Mechanisms in the reaction of palladium(II)–π-allyl complexes with aryl halides: evidence for NHC exchange between two palladium complexes. Chemistry: A European Journal 15 (29) , pp. 7063-7073. 10.1002/chem.200900373

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Abstract

A detailed experimental and DFT study (PBE level) of the reaction of [Pd(η3-C3H5)(tmiy)(PR3)]BF4 (tmiy=tetramethylimidazolin-2-ylidene, PR3=phosphane), precursors to monoligated Pd0 species, with aryl electrophiles yielding 2-arylimidazolium salt is reported. Experiments establish that an autocatalytic ligand transfer mechanism is preferred over PdIV and σ-bond metathesis pathways, and that transmetalation is the rate-determining step. Calculations indicate that the key step involves the concerted exchange of NHC and iodo ligands between two different PdII complexes. This is corroborated by experimental results showing the slower reaction of complexes containing the bulkier dipdmiy (dipdmiy = diisopropyldimethylimidazolin-2-ylidene).

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: Carbene ligands; Density functional calculations; Palladium; Transmetalation
Publisher: Wiley
ISSN: 0947-6539
Last Modified: 02 Jan 2018 21:26
URI: http://orca-mwe.cf.ac.uk/id/eprint/6083

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