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This article describes the synthesis, characterization, and reactivity of palladium(II) fluoride complexes containing sp2and sp3nitrogen-containing supporting ligands. Both cisand transcomplexes of general structure (N)(N′)PdII(R)(F) (R = Ar or CH3) as well as cis-(N)2PdII(F)2are reported. Crystallographic characterization of these molecules has allowed structural comparisons to related phosphine-ligated species. Furthermore, these studies have revealed that nitrogen-donor ligands support some of the longest and the shortest Pd–F bonds reported to date. The thermal decomposition of (N)(N′)PdII(R)(F) has also been examined, and no products of C–F bond-forming reductive elimination were obtained in any case. [ABSTRACT FROM AUTHOR]

This communication describes detailed investigations of the mechanism of the Pd-catalyzed C−H chlorination and acetoxylation of 2-o-tolylpyridine. Under the conditions examined, both reactions proceed via rate-limiting cyclopalladation. However, substrate and catalyst order as well as Hammett data indicate that the intimate mechanism of cyclopalladation differs significantly between PdCl2-catalyzed chlorination and Pd(OAc)2-catalyzed acetoxylation. [ABSTRACT FROM AUTHOR]