title: Magnesium and zinc complexes of a potentially tridentate beta-diketiminate ligand.
abstract: The synthesis of the unsymmetrically substituted beta-diketimine, 2-(2-methoxyphenylimino)-4-(2,6-diisopropylphenylamido)pent-2-ene, (BDI-2)H, is described and its complexation chemistry with magnesium and zinc is explored. Emphasis is placed on the preparation of alkoxide and amide derivatives for the ring-opening polymerisation of lactide; their behaviour as polymerisation initiators is compared to analogous compounds supported by the N,N'-bis(2,6-diisopropylphenyl) beta-diketiminate ligand, BDI-1. (BDI-2)H reacts with Me2Mg to give the bis(chelate) complex, (BDI-2)2Mg, 3. Magnesium alkyls supported by BDI-2 may be prepared by increasing the size of the alkyl group. Hence, lithiation of (BDI-2)H affords [(BDI-2)Li]2, 4; its subsequent treatment with iPrMgCl produces (BDI-2)MgiPr, 5. Aminolysis of complex using iPr2NH yields the amide complex, (BDI-2)MgNiPr2, 6. Zn(NTMS2)2 and ZnEt2 react with (BDI-2)H to give (BDI-2)Zn(NTMS2), 7, and (BDI-2)ZnEt, 8, respectively. The former is converted into the siloxide complex, (BDI-2)Zn(OSiPh3), 9, upon reaction with Ph3SiOH. The chloride derivative, (BDI-2)ZnCl, 10, has also been prepared via the reaction of ZnCl2 with 4. Crystallographic analysis of compounds, and reveals that the potential for (BDI-2) to bind in a tridentate manner is only realised with the more electrophilic metals Li and Mg. Compared to their (BDI-1) counterparts, complexes 6, 7 and 9 are more active, but less well-controlled, initiators for the ring-opening polymerisation of rac-lactide, a consequence of the diminished steric protection afforded by (BDI-2) relative to (BDI-1).
authors.affiliation: Department of Chemistry, Imperial College London, Exhibition Rd., London, UK SW7 2AZ.
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Dove
authors.forename: Vernon C
authors.initials: VC
authors.lastname: Gibson
authors.forename: Edward L
authors.initials: EL
authors.lastname: Marshall
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.forename: David J
authors.initials: DJ
authors.lastname: Williams
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D008274:Magnesium / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: C500587:2-(2-methoxyphenylimino)-4-(2,6-diisopropylphenylamido)pent-2-ene; D000475:Alkenes; D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; D008274:Magnesium; D015032:Zinc