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Rare-Earth Metal Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Heteroselective Ring-Opening Polymerization of rac-Lactide

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journal contribution
posted on 21.04.2008, 00:00 by Haiyan Ma, Thomas P. Spaniol, Jun Okuda
Monomeric yttrium and lutetium bis(phenolato) complexes [Ln(OSSO){N(SiHMe2)2}(THF)] (Ln = Y, Lu) were prepared from the reaction of silylamido complexes [Ln{N(SiHMe2)2}3(THF)2] with 1 equiv of tetradentate 1,ω-dithiaalkanediyl-bridged bis(phenol) (OSSO)H2 19 in moderate to high yields. In contrast to the rigid configuration of scandium analogues, the yttrium complexes 2b and 3b and the lutetium complex 3c that contain a C2 bridge between the two sulfur donors of the ligand are symmetric in solution. The monomeric nature of these complexes was indicated by an X-ray diffraction study of the yttrium complex 6b. The yttrium center in 6b is coordinated to the tetradentate [OSSO]-type ligand, one silylamido group and one THF ligand with the two oxygen donors of the [OSSO]-type ligand located trans. Corresponding bis(phenolato) silylamido complexes of larger rare-earth metals could not be obtained from similar reactions: Reaction of [La{N(SiHMe2)2}3(THF)2] with 1,2-xylylene-linked bis(phenol) gave a dinuclear lanthanum complex 6d of the formula [La2(OSSO)3] with two inequivalent eight-coordinate metal centers. The yttrium and lutetium complexes efficiently initiated the ring-opening polymerization (ROP) of lactides in THF. The heteroselectivity during the ROP of rac-lactide was enhanced when the steric demand of the bis(phenolato) ligand was increased, either by extending the bridge length or by introducing bulky ortho-substituents in the phenoxy units. A C3 bridge within the ligand backbone is essential to allow configurational interconversion of the active site between Λ and Δ configuration during polymerization, allowing accommodation of both enantiomers of the monomer in an alternating fashion.