New lanthanoid biphenolate complexes, their further reactivity with trimethylaluminium and catalytic activity for the polymerisation of rac-lactide

Abstract

A series of rare earth biphenolate complexes of the general form [Ln(mbmp)(mbmpH)(thf)₃] (Ln = Y (1), Nd (2), Gd (3), Dy (4), Er (5), Tm (6) and Lu (7)) have been synthesised by redox transmetallation/protolysis (RTP) from the free rare earth metal, Hg(C₆F₅)₂ and 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH₂). The rare earth metal is six coordinate with one chelating biphenolate mbmp²⁻ ligand and one unidentate monophenolate mbmpH⁻ ligand. The yttrium complex, when crystallised from hot toluene or deuterated benzene, loses a coordinated thf and exhibits coordination through all three phenolate oxygen atoms, as well as the oxygen of the phenol, yielding two solvates [Y(mbmp)(mbmpH)(thf)₂]·nsolv (solv = PhMe, n = 1 (8a) or C₆D₆, n = 2 (8b)). Of these rare earth complexes, the yttrium derivative (1) yielded the heterobimetallic complex [AlMe₂Y(mbmp)₂(thf)₂] (9) when treated with trimethylaluminium, whereas all other complexes produced the transmetallation product [AlMe(mbmp)(thf)] (11). The dinuclear dysprosium complex [Dy₂(mbmp)₃(thf)₃] (10) was isolated alongside 11 from the reaction of 4 with trimethylaluminium, suggesting trimethylaluminium instigates a redistribution reaction. The ROP activity of the mononuclear neodymium, dysprosium, lutetium, and aluminium complexes towards rac-lactide in toluene at 70 °C was found to be poor compared to rare earth complexes of monodentate aryloxides, but increased with increased rare earth ion size.