Insertion reactions of unsymmetrical ester-activated alkynes with o-benzylamine palladacycles: A regioselectivity study

Amy E. Kelly, Stuart A. Macgregor, Anthony C. Willis, John H. Nelson, Eric Wenger*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    27 Citations (Scopus)

    Abstract

    The regioselectivities of the insertion reactions of RC≡CCO2Et (R=Ph, CF3) into the aryl-palladium bond of several five-membered, ortho-palladated dimethylbenzylamine complexes, [PdCl(C6H4CH2NMe2-κC,N)] 2 (1), [PdCl(C6H4CH2NMe2-κC,N)(L)] [L=PEt3 (2), DMPP (3)], [Pd(C6H4CH2NMe2-κC,N) (NCMe)(L)]PF6 [L=MeCN (4), PEt3 (9), DMPP (5)], [Pd(OSO2CF3)(C6H4CH 2NMe2-κC,N)(DMPP)] (6), [Pd(C6H4CH2NMe2-κC,N) (solvent)]PF6 (7) and [Pd(C6H4CH2NMe2-κC,N) (DMPP)(solvent)]PF6 (8), have been compared with the help of multinuclear NMR spectroscopy. In general, the carboxylate group in the resulting seven-membered palladacycles is preferentially located next to the phenyl group of the benzylamine moiety, but this substitution pattern can be reversed by use of complexes containing electron-deficient and/or coordinatively-unsaturated palladium centres. A mechanism, based both on the experimental results described in this paper and on DFT computations, is proposed.

    Original languageEnglish
    Pages (from-to)79-97
    Number of pages19
    JournalInorganica Chimica Acta
    Volume352
    DOIs
    Publication statusPublished - 6 Aug 2003

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