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Palladium(II) Agostic Complex: Exchange of Aryl-Pd and Alkyl-Pd Bonds

Thomas, H.R., Deeth, R.J., Clarkson, G.J. and Rourke, J.P. ORCID: 2011. Palladium(II) Agostic Complex: Exchange of Aryl-Pd and Alkyl-Pd Bonds. Organometallics 30 (21) , pp. 5641-5648. 10.1021/om200451v

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Cyclopalladation of 2-tbutyl-6-(4-fluorophenyl)pyridine with palladium acetate cleanly gives cyclometalated complex 3 with an aryl–Pd bond. Replacement of the acetates by chloride gives the monomeric species 4 with a crystal structure confirming the presence of an agostic interaction from the alkyl group. Reaction of 3 with Na(acac) initially gives the monomeric acac complex 5 which maintains the aryl–Pd bond. Complex 5 shows fluxional behavior of the acac group, and this provides a pathway for its isomerization to complex 6 which has an alkyl–Pd bond; complex 6 was characterized crystallographically. Reaction of agostic 4 with triphenylphosphine gives an initial complex that maintains the aryl–Pd bond, but this complex isomerizes to crystallographically characterized 8 which has an alkyl–Pd bond.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 0276-7333
Last Modified: 21 Jun 2023 12:30

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