Synthesis, X-ray structures, and syndiospecific polymerization behavior of styrene of new (pentamethylcyclopentadientyl) titanatranes containing modified tetradentate triethanolamine ligands

A series of monomeric pentamethylcyclopentadienyltitanatranes, [n = 0, 1; n = 1, 2; n = 2, 3], were synthesized by the reaction of Cp∗TiCl3 with corresponding triethanolamines such as (HOCH2CH2)nN(CH2CMe2OH)3 − n (n = 0, L1H3; n = 1, L2H3; n = 2, L3H3), which varied by the number of CMe2 groups adjacent to an OH functionality from 3 (L1H3) to 2 (L2H3) to 1 (L3H3), in the presence of NEt3. All complexes were characterized by elemental analysis and solution 1H and 13C{1H} NMR spectroscopy. Moreover, their solid state structures, which are slightly distorted three-legged piano stool geometry, have been confirmed by single crystal X-ray diffraction analysis. On activation with methylaluminoxane (MAO), these complexes showed good catalytic activity for the polymerization of styrene producing syndiotactic polystyrene (SPS) with high molecular weights. Compounds 1 and 2 bearing more than two pairs of methyl substituents on the side arms of triethanolamines showed the enhanced catalytic activities as the polymerization temperature went up from 50 °C to 110 °C, whereas less bulky complexes 3 and Cp∗Ti(OCH2CH2)3N (4) gave the decreased activities as polymerization temperature rose. Unlike 3 and 4, complexes 1 and 2 in the presence of MAO as a cocatalyst gave SPS with controlled bimodal molecular weight distribution. Bimodal properties were much distinct at low polymerization temperature.

Graphical abstractNew half-titanocenes, Cp∗Ti(OCH2CH2)nN(CH2CMe2O)3 − n [n = 0, 1; n = 1, 2; n = 2, 3] were prepared from Cp∗TiCl3 with the corresponding alcohols in the presence of triethylamine. X-ray analysis shows that 1–3 have slightly distorted trigonal–bipyramidal geometry around Ti. These complexes exhibited good catalytic activities for syndiospecific styrene polymerization in the presence of MAO. Interestingly, complexes 1 and 2 gave syndiotactic polystyrenes with controlled bimodal molecular weight distribution.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Trialkanolamine ligands (HOCH2CH2)nN(CH2CMe2OH)3 − n (n = 0–2) were used as a ligand. ► New monomeric titanatranes were prepared. ► Titanatrane complexes were used as catalysts for syndiospecific polymerization of styrene. ► Syndiotactic polystyrene with bimodal MWD was obtained.