Iodo(aryl)palladium complexes, [PdI{C 6 H 3 (CF 3 ) 2 -3,5}(N-N)] (N-N ) tmeda, bpy, 4,4′dimethyl-2,2′-bipyridine (Me 2 bpy)), react with AgBF 4 in CH 3 CN, acetone, and THF to yield stable cationic arylpalladium complexes [Pd{C 6 H 3 (CF 3 ) 2 -3,5}(N-N)(solv)]BF 4 . A similar reaction of AgBF 4 with [PdI(C 6 H 3 Me 2 -3,5)(bpy)] in CH 3 CN gives [Pd(C 6 H 3 Me 2 -3,5)(bpy)-(CH 3 CN)]BF 4 . The complex does not change its NMR spectrum for 1 h at room temperature in CD 3 CN but undergoes decomposition upon dissolution in acetone to release 3,3′,5,5′tetramethylbiphenyl. Addition of AgBF 4 to acetone or THF solutions of [PdI(Ar)(bpy)] (Ar ) Ph, C 6 H 3 Me 2 -3,5) and of [PdI(Ar)(Me 2 bpy)] (Ar ) C 6 H 4 OMe-4, C 6 H 3 Me 2 -3,5) does not lead to isolation of the cationic arylpalladium complexes and causes intermolecular coupling of the aryl ligands to yield the corresponding biaryls. The reaction of AgBF 4 with [PdI(C 6 H 3 Me 2 -3,5)(bpy)] in the presence of an excess amount of dimethyl acetylenedicarboxylate (DMAD) in CH 3 CN gives [Pd(CZdCZ-CZdCZ-C 6 H 3 Me 2 -3,5)(bpy)(CH 3 CN)]BF 4 (Z ) COOMe) via insertion of two acetylene molecules into the Pd-aryl bond. A similar reaction in acetone or THF causes insertion of three DMAD molecules into the Pd-aryl bond and cyclization of the formed Pd-(CZdCZ) 3 -Ar group to give the product containing a cyclopentadiene structure in the ligand. [PdI(CZdCZ-C 6 H 3 Me 2 -3,5)(bpy)] reacts with AgBF 4 in CH 3 CN to form a cationic complex, [Pd(CZdCZ-C 6 H 3 Me 2 -3,5)(bpy)(CH 3 CN)]BF 4 . A series of cationic Pd complexes, formed through insertion of one, two, and three alkyne molecules into the Pd-aryl bond, are characterized by X-ray crystallography or NMR spectroscopy. Phenylallene reacts with [PdI(C 6 H 3 Me 2 -3,5)(bpy)] in the presence of AgBF 4 to give [Pd{η 3 -CH 2 C-(C 6 H 3 Me 2 -3,5)CHPh}(bpy)]BF 4 via insertion of the CdC double bond of the allene into the Pd-C bond of the cationic arylpalladium complex. The π-allylpalladium complex crystallizes exclusively in a form with a syn-oriented phenyl substituent but exists in solution as a mixture of the isomers with a syn or anti phenyl substituent.