A series of new titanium(IV) complexes with symmetric or asymmetric cis-9,10-dihydrophenanthrenediamide ligands, cis-9,10-PhenH(2)(NR)(2)Ti((OPr)-Pr-i)(2) [PhenH(2) = 9,10-dihydrophenanthrene, R = 2,6-(Pr2C6H3)-Pr-i (2a), 2,6-Et2C6H3(2b), 2,6-Me2C6H3 (2c)], cis-9,10-PhenH(2)(NR1)(NR2)Ti((OPr)-Pr-i)(2) [R-1 = 2,6-Pr2C6H3, R-2 = 2,6-Et2C6H3 (2d); R-1 = 2,6-(Pr2C6H3)-Pr-i, R-2 = 2,6-Me2C6H3 (2e)), and [cis-9,10-phenH(2)(NR1)(2)][o-C6H4(CH=NR2)](TiOPr)-Pr-i [R-1 = 2,62Pr(2)C(6)H(3), R-2 = 2,6-Et2C6H3 (3a); R-1 = 2,6-(Pr2C6H3)-Pr-i, 2,6-Me2C6H3 (3b)], have been synthesized from the reactions of TiCl2((OPr)-Pr-i)(2) with o-C6H4(CH=NR)Li [R = 2,6-(Pr2C6H3)-Pr-i, 2,6-Et2C6H3, 2,6-Me2C6H3]. The symmetric complexes 2a-2c were obtained from the reactions of TiCl2((OPr)-Pr-i)(2) with 2 equiv of the corresponding o-C6H4(CH=NR)Li followed by intramolecular C-C bond-forming reductive elimination and oxidative coupling processes, while the asymmetric complexes 2d-2e were formed from the reaction of TiCl2((OPr)-Pr-i)(2) with two different types of o-C6H4(CH=NR)Li sequentially. The complexes 3a and 3b were also isolated from the reactions for complexes 2d and 2e. All complexes were characterized by H-1 and C-13 NMR spectroscopy, and the molecular structures of 2a, 2b, 2e, and 3a were determined by X-ray crystallography.