Cis-1,4-Polymerization of Isoprene by 1,3-Bis(oxazolinymethylidene)isoindoline-Ligated Rare-Earth Metal Dialkyl Complexes.

ABSTRACT

A series of novel chiral nonmetallocene pincer-type rare-earth metal dialkyl complexes bearing the chiral monoanionic tridentate C2-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI-H) ligand (BOXMI)Ln(CH2SiMe3)2 1⁻3 (1 Ln = Sc, yield = 57%; 2 Ln = Lu, yield = 55%; 3 Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare-earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one BOXMI ligand and two trimethylsilylmethyl ligands, adopting a distorted trigonal bipyramidal configuration. In the presence of a cocatalyst such as borate and AlR3, these complexes 1⁻3 exhibit high activities of up to 6.8 × 104 (g of polymer)/(molLn h) and high cis-1,4 selectivities of up to 97% in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with heavy molecular weights (Mn of up to 710,000 g/mol) and bimodal molecular weight distributions (Mw/Mn = 2.0⁻4.5).