A series of palladium and platinum complexes containing inversely polarized phosphaalkenes (Me2N)(R)C=PR' (R = H, R' = Mes*, 2; R = Me, R' = Mes*, 3; R = H, R' = Mes, 4), exhibiting different steric and electronic environments, have been synthesized. Ligand 2 coordinates in 1-P fashion to either palladium (PdCl2(1-P)2, 5) or platinum (cis-Pt(Cl)2(1-P)2, 6; trans-Pt(Cl)2(1-P)2, 7). The equimolar reaction of 3 with Pd(COD)Cl2 afforded a mixture in 3/1 ratio of cyclopalladated dimeric complexes [PdCl(2-P,C-CH2N(Me)CH=PMes*)]2, 9 (cis isomer) and 9' (trans isomer). The latter was characterized by X-ray diffraction. The less hindered ligand 4 acts as bridging phosphido-like ligand with both palladium (-P-[PdCl2(MesP=CH(NMe2))]2, 11) and platinium (-P-[PtCl2(MesP=CH(NMe2))]2, 12). In the platinum case, the reaction of two or more equivalents of the ligand 4 gave a mixture of the complex containing 2 ligands/Pt and the cationic complex with 3 ligands/Pt, 13. This complex was isolated from the reaction of 3.5 equiv of 4 with the Pt precursor.