Palladium(II) complexes containing bidentate cyclometalated C∼N chelating ligands are shown to
react with PhINTs at room temperature to insert “NTs” into the Pd−C bond. This “NTs” insertion
reaction has been applied to palladacyclic complexes of azobenzene, benzo[h]quinoline, and 8-ethylquinoline. The newly aminated organic ligands can be liberated from the metal center by protonolysis
with trifluoroacetic acid or HCl.
This communication describes studies of oxidatively induced C-C bond-forming reductive elimination from ((t)Bu(2)bpy)Pd(II)(Me)(2). With the outer-sphere oxidant ferrocenium, the data are consistent with a mechanism involving Pd(III) and Pd(IV) intermediates, with C-C bond formation occurring from the latter. The reaction with Ag(+) appears to proceed via a Pd-Ag(+) adduct, which then undergoes inner sphere electron transfer to generate Pd(III). In contrast, the slower benzoquinone reaction forms ethane by a different pathway that does not involve methyl group scrambling and generates Pd(0) products.
This article describes the high-yielding and selective oxidatively induced formation of ethane from mono-methyl palladium complexes. Mechanistic details of this reaction have been explored via both experiment and computation. On the basis of these studies, a mechanism involving methyl group transmetalation between Pd(II) and Pd(IV) interediates is proposed.
This report describes the development of two photocatalytic methods for the pyridination of electron rich arenes. First, an S N Ar-type reaction between aryl halides and pyridine is developed and optimized. This transformation affords selective substitution of C(sp 2 )− halogen over C(sp 2 )−OR bonds to afford arylpyridinium products under anaerobic conditions. Under complementary aerobic conditions, analogous substrates are shown to undergo oxidative C(sp 2 )−H pyridination.
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