Research output: Contribution to journal › Article › peer-review
Journal | Organometallics |
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Date | Published - 14 Sep 2015 |
Issue number | 17 |
Volume | 34 |
Number of pages | 11 |
Pages (from-to) | 4376-4386 |
Original language | English |
The effect of fluorine substituents on the regioselectivity of intramolecular reactions of mono- and difluorinated N,N-dimethylbenzylamines (1a-f) at palladium, to form palladacycles di-μ-acetatobis[o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (2a-f) and di-μ-chlorobis[o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (3a-e), has been investigated. When fluorinated substrates with two sites available for the C-H functionalization (1c and 1e) undergo cyclopalladation via a CMD mechanism (acetate-bridged palladacycles), they do not exhibit regioselectivity. In contrast, the same substrates exhibit complete regioselectivity for the C-H functionalization para to fluorine in cyclopalladation reactions that proceed via an S<inf>E</inf>Ar mechanism (involving chloride-bridged palladacycles). X-ray crystal structures were obtained for all the palladacycles synthesized, and a structural analysis showed that the number and the position of the fluorine atoms on the aromatic ring have a marked effect on the "clamshell" structure of the acetate-bridged palladacycles. By contrast, there is no great variation in the structures of the planar chloride-bridged palladacycles.
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