Reactions of [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)PdCl] 2 (1) with (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP), bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP), and tris(2,6-dimethoxyphenyl)phosphine (TDMPP) gave the corresponding complexes [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)PdCl(L)] (2a: L=MDMPP; 2b: L=BDMMP; 2c: L=TDMPP). Reactions of 2 with NaPF 6 led to replacement of the Cl atom with the methoxy-O atom to form the corresponding complexes [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)Pd(L)](PF 6 ) (3). On treatment of 3 with HCl (aq), protonation occurred at the N atom in 3 to give [(C 6 H 4 CH 2 NHMe 2 -C 2 )PdCl(L)] (5). Based on X-ray structural analyses of 2c, 3a, 3b, 5a and 5c, complexes (2b, 2c, 3b, 3c, 5b and 5c) bearing BDMPP and TDMPP ligands have square-pyramidal structures with a P-O coordination in the axial position and complexes (2a, 3a and 5a) bearing MDMPP have square planar structures. When a complex bearing triphenylphosphine [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)PdCl(PPh 3 )] was treated with NaPF 6 , [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)Pd(PPh 3 )(O 2 H)](PF 6 ) (4) bearing a H 2 O ligand was obtained. The reaction with HCl (aq) led to a cleavage of a Pd-C bond to give [PdCl 3 (PPh 3 )][PhCH 2 NHMe 2 ] (6). X-ray analyses of 4 and 6 were also carried out. Reactions of 1 or 2a with mesityl isocyanide (MesNC) proceeded with replacement of a Cl atom with isocyanide and insertion of isocyanide to produce [(C 6 H 4 CH 2 NMe 2 -C 2 ,N)PdCl(MesNC)] (7) and [C 6 H 4 CH 2 NMe 2 -C 2 )PdCl(MesNC) 2 ] (8).