Reaction of trans-Pd(PPh 3) 2I(CH 3) ( 1a) with 2,6-xylyl isocyanide in a 1:1 molar ratio led to a spontaneous insertion of isocyanides into a PdC bond to give the tris-imino insertion product 2a. The structure was determined by an X-ray analysis. The crystals are triclinic with space group P1 ( a = 14.638(9), b = 15.662(7), c = 7.895(3) Å, α = 85.06(6), β = 82.84(4), γ = 102.4(4)°, and Z = 2; R = 0.066 for 2076 independent reflections with F 0 > 5σ( F 0). The tris-imino group acts as a bidentate ligand through C- and N-coordinations. The 2-methyl-1-naphthyl complex, trans-Pd(PPh 3)Br(2-CH 3C 10H 9) reacted with 2,6-xylyl isocyanide to give a bis-imino complex containing μ 2-Br bridging ligands. Using p-nitirophenyl isocyanide, the reaction produced a mono-imino compound. Reaction of 2a with CuCl 2 gave a mixed metal complex, in which the copper(II) atom is coordinated to two neighbouring imino-nitrogens.