A new chiral half-titanocene complex, [CpTiCl2(O-(S)-2-Bu)], is synthesized and characterized by H-1 and C-13 NMR spectroscopy. This complex is employed for the coordination polymerization of n-butyl and n-hexyl- isocyanate leading to chiral polymers, as revealed by their CD spectra. Only the left-handed helix is produced, due to the chiral (S -2-butoxy group, which is bound to the polymer chain end. The polymerization of 3-(triethoxysilyl) propyl isocyanate produces less soluble polymers. On the other hand, phenyl isocyanate reacts slowly with the complex leading quantitatively and selectively to triphenyl isocyanurate. 2-Ethylhexyl isocyanate is slowly and selectively cyclotrimerized in the presence of thehalf-titanocene complex. However, a statistical copolymer of 2-ethylhexyl isocyanate and hexyl isocyanate is produced. The reaction of benzyl isocyanate with the complex leads to a mixture of low molecular weight polymer and cyclotrimer. The polymers are characterized using SEC, NMR, and CD spectroscopy and their thermal properties are investigated by TGA/DSC analysis. (C) 2015 Wiley Periodicals, Inc.