Chemistry of BDI*M2+ complexes (M = Mg, Zn) and their role in lactide polymerization where BDI* is the anion derived from methylenebis(C-(t)Bu, N-2,6-diisopropylphenyl)imine BDI*H.

The bulky diimine CH(2){C((t)Bu)N-2,6-Pr(i)(2)C(6)H(3)}(2), BDIH, is shown to exist in two isomers trans-trans, 1a and cis-trans, 1b that interconvert slowly on the NMR time-scale. Treatment of the diimine with (n)BuLi in hexane proceeds slowly to give the lithium beta-diketoiminate LiBDI, 2, which upon hydrolysis yields the eneimine tautomer of BDIH which has been characterized by X-ray studies in three rotamers, 3a, 3b and 3c. Dialkylmetal compounds (M = Mg, R = Bu; M = Zn, R = Et) react with either 1 or 3 in hydrocarbon and ether solvents to give BDIMg((n)Bu)THF, 4, and BDIZnEt, 5, which have been structurally characterized. M(N(SiMe(3))(2))(2) compounds where M = Mg, Zn or Ca failed to react with either 1 or 3 in hydrocarbon solvents. The reactions between ZnCl(2) and 2 yield BDIZnCl, 6, and a further reaction with LiNMe(2) yields BDI*ZnNMe(2), 7. The compounds 5 and 6 are shown to contain trigonal planar, M(2+) ions. Compounds 4, and 7 initiate ring-opening polymerization, ROP, of rac-lactide to give atactic polylactide, PLA. The rate of ROP depends on the metal M = Mg > Zn and is slower than that observed for the related beta-diketoiminate complexes where the bulky-(t)Bu group is replaced by Me.