Titanium(IV) hydrocarbyl compounds containing chiral bis(amide) ligands derived from (±)-trans-1,2-(NHSiR3)2-cyclohexanes (6a−c: SiR3 = SiMe3 (a), SiMe2Ph (b), SiMePh2 (c) are described. The reaction of (±)-trans-1,2-diaminocyclohexane with SiR3Cl and NEt3 affords diamines 6a−c in 60−80% yield. Double deprotonation of 6a−c with 2 equiv of n-BuLi yields the dilithio salts Li2[(±)-trans-1,2-(NSiR3)2-cyclohexane] (7a−c) in 70−97% yield. The reaction of 7a,b with TiCl4(THF)2 in toluene yields mixtures of {(±)-trans-1,2-(NSiR3)2-cyclohexane}TiCl2 (8a,b) and bis(ligand) complexes {trans-1,2-(NSiR3)2-cyclohexane}2Ti (9a,b; mixture of diastereomers). The reaction of 7c with TiCl4 yields {(±)-trans-1,2-(NSiMePh2)2-cyclohexane}TiCl2 (8c; 15% isolated yield). The reaction of 6a,b and Ti(CH2Ph)4 yields {(±)-trans-1,2-(NSiR3)2-cyclohexane}Ti(CH2Ph)2 (10a,b) cleanly, but these species are difficult to isolate due to their high solubility. Iodinolysis of 10a,b with I2 yields {(±)-trans-1,2-(NSiR3)2-cyclohexane}TiI2 (11a...