The reaction of [PdI{C,N-C(═NHXy)C6H4NH2-2}CNXy]TfO with XyNC (1:2, TfO = CF3SO3, Xy = C6H3Me2-2,6) gives the cationic carbene complex [PdI{C,C-C(═NHXy)C6H4{NHC(NHXy)}-2}CNXy]TfO (4), while that of [PdCl2{C(═NHXy)C6H4NH2-2}] with isocyanides (1:1, 50–60 °C) gives the neutral carbene complexes [PdCl2{C,C-C(═NHXy)C6H4{NHC(NHR)}-2}] (R = tBu (8), Xy (9)), from which mono- and dicationic derivatives [PdCl{C,C-C(═NHXy)C6H4{NHC(NHXy)}-2}L]X (L = XyNC, X = TfO (10); L = PPh3, X = Cl (11)) and [Pd{C,C-C(═NHXy)C6H4{NHC(NHXy)}-2}(CNXy)2](TfO)2 (12), respectively, have been isolated. Dehydrochlorination of complex 9 with TlTfO and NaOAc (1:2:2) or with NEt3 (1:1) affords the dinuclear complexes [(PdX)2{μ-N,C,C-C(═NXy)C6H4{NHC(NHXy)}-2}2] (X = OAc (13), Cl (14)), which in turn react with PPh3 to give [PdX{C,C-C(═NXy)C6H4{NHC(NHXy)}-2}PPh3] (X = OAc (15), Cl (16)). Oxidative addition of 2-iodobenzoic acid to 13 leads to the Pd(IV) complex [{PdI(C6H4CO2-2)}2{μ-N,C,C-C(═NXy)C6H4{NHC(NHXy)}-2}2] (17), while the reaction of 14 with PhICl2 affords the Pd(III) derivative [(PdCl2)2{μ-N,C,C-C(═NXy)C6H4{NHC(NHXy)}-2}2] (18). The crystal structures of 4, 9, and 12 have been determined, and the atomic connectivity in 18 has been established.