Selective C8-Metalation of Purine Nucleosides via Oxidative Addition

8-Bromo-2′-deoxy-3′,5′-di-O-acetylguanosine (1), 8-bromo-2′,3′,5′-tri-O-acetylguanosine (2), 8-bromo-2′-deoxy-3′,5′-di-O-acetyladenosine (3), and 8-bromo-2′,3′,5′-tri-O-acetyladenosine (4) react with [Pd­(PPh3)4] via a C8–Br oxidative addition to give the C8-palladated azolato complexes [5]–[8] featuring an unprotonated N7 ring nitrogen atom. The complexes feature diastereotopic trans-disposed triphenylphosphine ligands, which allowed the determination of 2 J PP for complexes of the type trans-[PdL2(PPh3)2] (2 J PP = 442 Hz for [7]). In addition, two complex molecules of [7] form a trans-Watson–Crick/Hoogsteen AA base pair in the solid state. N7-protonation of the guanosine-derived complexes [5] and [6] with HBF4·Et2O and of adenosine-derived complexes [7] and [8] using lutidinium triflate yields complexes [9]­BF4 and [10]­BF4 and complexes [11]­OTf and [12]­OTf bearing protic NH,NR-NHC ligands derived from guanosine and adenosine, respectively.