Highly <i>cis</i>-1,4 Selective Polymerization of Dienes with Homogeneous Ziegler−Natta Catalysts Based on NCN-Pincer Rare Earth Metal Dichloride Precursors

Abstract

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2NCH)2-C6H3)LnCl2(THF)2 (Ln = Y, R = Me (1), Et (2), iPr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C6H3-R2NCH)2-C6H3Li and LnCl3(THF)1∼3.5. These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a κC:κN:κN‘ tridentate mode, adopting a meridional geometry. Complexes 1−6, 9−11, and 13 combined with aluminum tris(alkyl)s and [Ph3C][B(C6F5)4] established a homogeneous Ziegler−Natta catalyst system, which exhibited high activities and excellent cis-1,4 selectivities for the polymerizations of butadiene (Tp = 25 °C, 99.9%; 0 °C, 100%) and isoprene (Tp = 25 °C, 98.8%). Remarkably, such high cis-1,4 selectivity almost remained at elevated polymerization temperatures up to 80 °C and did not vary with the type of the central lanthanide element, however, which was influenced obviously by the ortho substituent of the N-aryl ring of the ligands and the bulkiness of the aluminum alkyls. The Ln-Al bimetallic cations were considered as the active species. These results shed new light on improving the catalytic performance of the conventional Ziegler−Natta catalysts for the specific selective polymerization of dienes