title: Synthesis and structures of complexes with axially chiral isoquinolinyl-naphtholate ligands.
abstract: The synthesis of axially chiral ligands 1-(3',6'-di-t-butyl-2'-hydroxy-1'-naphthyl)-3-R-isoquinoline (R = H, Pr(i), Bu(t)) (LR-H) is described. Ligands with unsubstituted isoquinolinyl rings tend to give 1:2 metal complexes. The syntheses and crystal structures of Li2(LH)2(THF)2 (9), (LH)2Ti(OPr(i))2 (12), Zn(LH)2 (13) and [Mg(LH)2]2 (14) are reported. Complex formation is highly stereoselective; the ligands in 1:2 complexes have the same stereochemistry (i.e. R,R and S,S but not R,S), whereas in the binuclear magnesium compound 14 the bridging and non-bridging ligands LH have opposite stereochemistry. The reaction of LH-H with Pd(acac)2 afforded the N,O chelate Pd(acac)(LH) (10), whereas towards K2PtCl4 the same ligand acts as an N-donor only, to give trans-PtCl2(LH-H)2 (11) in which the OH groups are hydrogen-bonded to one of the two chloride ligands. The more bulky ligand with a t-butyl substituent in the 3-position of the isoquinolinyl ring reacts with zinc and magnesium bis(amides) to give the mixed-ligand species (LBu)ZnN(SiMe3)2 and (LBu)MgN(SiMe3)2, respectively, which catalyse the ring-opening polymerisation of epsilon-caprolactone (CL) and rac-lactide (LA).
authors.affiliation: Wolfson Materials and Catalysis Centre, School of Chemical Sciences and Pharmacy, University of East Anglia, Norwich, NR4 7TJ.
authors.forename: Ruth H
authors.initials: RH
authors.lastname: Howard
authors.forename: Carlos
authors.initials: C
authors.lastname: Alonso-Moreno
authors.forename: Lewis M
authors.initials: LM
authors.lastname: Broomfield
authors.forename: David L
authors.initials: DL
authors.lastname: Hughes
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Wright
authors.forename: Manfred
authors.initials: M
authors.lastname: Bochmann
mesh_terms: D018360:Crystallography, X-Ray; D007546:Isoquinolines / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009284:Naphthols / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D007546:Isoquinolines; D008024:Ligands; D009284:Naphthols; D009942:Organometallic Compounds