A number of applications have been found for the variety complexes of Pd(II) and Pt(II) due to their marked catalytic activities. This study is intended to examine the seven and eight-membered novel complexes which have been prepared by P-N-C-C-O-P and P-N-C-C-C-O-P backbone ligands. The air-stable complexes [M = Pd (1a, 3a), Pt (1b, 3b)] containing aminophosphine-phosphinite metallocyclic rings were obtained with high yields. All the compounds were characterized by P-31{H-1}, C-13{H-1} and H-1 NMR spectroscopy, FTIR spectroscopy and elemental analysis. Furthermore, the structure of complexes (1a and 3a) were determined by X-ray crystallography. The novel complexes (1a and 3a) are very effective catalysts on Suzuki-Miyaura cross-coupling reactions of various aryl chlorides and aryl bromides with phenylboronic acid.