title: 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.
abstract: The bulky diimine CH(2){C((t)Bu)N-2,6-Pr(i)(2)C(6)H(3)}(2), BDI*H, 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 BDI*H 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 BDI*Mg((n)Bu)THF, 4, and BDI*ZnEt, 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 BDI*ZnCl, 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.
authors.affiliation: Department of Chemistry, The Ohio State University, Columbus, OH 43210, USA.
authors.forename: Carla N
authors.initials: CN
authors.lastname: Ayala
authors.forename: Malcolm H
authors.initials: MH
authors.lastname: Chisholm
authors.forename: Judith C
authors.initials: JC
authors.lastname: Gallucci
authors.forename: Clemens
authors.initials: C
authors.lastname: Krempner
mesh_terms: D000838:Anions / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011091:Polyesters / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D000838:Anions; D056831:Coordination Complexes; D007097:Imines; D009942:Organometallic Compounds; D011091:Polyesters; C033616:poly(lactide); D008274:Magnesium; D015032:Zinc