6533b83afe1ef96bd12a781b

RESEARCH PRODUCT

Synthesis and Reactivity toward Isonitriles of (2-Aminoaryl)palladium(II) Complexes

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Mixtures of “Pd(dba)2” (dba = dibenzylideneacetone) and 2,2‘-bipyridine (bpy; 1:2) or N,N,N‘,N‘-tetramethylethylenediamine (tmeda; 1:1) react with 2-bromo-4-nitroaniline to give [Pd{C6H3NH2-2-NO2-5}Br(N−N)] (N−N = bpy (1b), tmeda (1b‘)). Reactions of 2-iodoaniline with mixtures of “Pd(dba)2” and isonitriles RNC (R = C6H3Me2-2,6 (Xy), 2:1:2 molar ratios; R = tBu, 2.9:1:2 molar ratios) result in the formation of the complexes [Pd{κ2C,N-C(NXy)C6H4NH2-2}I(CNXy)] (2a) and trans-[Pd{C(NtBu)C6H4NH2-2}I(CNtBu)2] (3a*). The reactions of [Pd{C6H4NH2-2}I(bpy)] and 1b‘ with RNC give the complexes trans-[Pd{C(NR)C6H3NH2-2-Y-5}}X(CNR)2] (Y = H, X = I, R = Xy (3a), tBu (3a*); Y = NO2, X = Br, R = Xy (3b), tBu (3b*)). Complexes 3 react with Tl(TfO) (TfO = CF3SO3) to give decomposition products, with the exception of 3a, which gives the cyclopalladated complex cis-[Pd{κ2C,N-C(NXy)C6H4NH2-2}(CNXy)2]TfO (4a). Complex 2a or 3 reacts with Tl(TfO) in the presence of the corresponding ligand, L or L2, to give the cationic compl...