New unsymmetrical ($alpha$-Diimine)nickel(II) catalysts having different pendent groups at the ortho positions on aromatic rings were synthesized and subjected to propylene polymerizations with MAO (methylaluminoxane). Structural analyses of the resulting polypropylenes by $^1H;and;^{13}C;NMR$ showed that the ortho substituents on aromatic rings of ($alpha$-diimine)nickel(II) catalyst affected significantly the polypropylene microstructure. While $C_s$ symmetric catalyst afforded a syndiotactic polypropylene (rr triad content=66%) due to the syndiospecific chain end control, $C_1$ symmetric catalysts produced much less stereoregular polypropylenes (rr triads content <50%), presumably because of collision of the isospecific site control with the syndiospecific chain end control.