NDLI: Zinc complexes supported by claw-type aminophenolate ligands : synthesis, characterization and catalysis in the ring-opening polymerization of rac-lactide

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Zinc complexes supported by claw-type aminophenolate ligands : synthesis, characterization and catalysis in the ring-opening polymerization of rac-lactide

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Zinc complexes supported by claw-type aminophenolate ligands : synthesis, characterization and catalysis in the ring-opening polymerization of rac-lactide

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ma, Haiyan Zhang, Xingyu Yang, Yang Song, Shaodi
Description	Author Affiliation: Song S ( Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Shanghai, People's Republic of China.)
Abstract	A series of zinc silylamido complexes bearing claw-type multidentate aminophenolate ligands , $[LZnN(SiMe_{3})_{2}]$ (L = $–OAr^{1}-CH_{2}N[(CH_{2})_{n}NR_{2}]CH_{2}Ar^{2},$ n = 2 or 3; R = Me or Et (1a–3a, 5a, 7a and 8a); L = $–OC_{6}H_{2}-4,6-^{t}Bu_{2}-2-CH_{2}N[(CH_{2})_{2}OMe]_{2}$ (9a)), have been synthesized via the reaction of $Zn[N(SiMe_{3})_{2}]_{2}$ and 1 equiv. of corresponding aminophenol . The reaction of $Zn[N(SiMe_{3})_{2}]_{2}$ with the proligand $L^{6}H$ (2-{N-(2-methoxybenzyl)-N-[3-(N′,N′-dimethylamino)propyl]aminomethyl}-4-methyl-6-tritylphenol) resulted in the formation of bisphenolate zinc complex 6 regardless of the stoichiometric ratio of the two starting materials. Complex 4b with an initiating group of 3-tert-butyl-2-methoxy-5- methylbenzyloxy was obtained and further studied via the X-ray diffraction method to be monomeric. Zinc ethyl complex 2c was also prepared from the reaction of $ZnEt_{2}$ and 1 equiv. of proligand $L^{2}H$ as the representative complex with an alkyl initiating group. All zinc silylamido complexes efficiently initiated the ring-opening polymerization of rac- lactide in the presence or absence of isopropanol at ambient temperature. The steric and electronic characteristics of the ancillary ligands significantly influenced the polymerization performance of the corresponding zinc complexes. The introduction of bulky ortho- substituents on the phenoxy moiety resulted in an apparent decrease of catalytic activity while a slightly enhanced isotactic selectivity. Meanwhile, the elongation of the pendant amine arm to three-carbon-atom linkage led to significant decline of the catalytic activity in the absence of isopropanol . The zinc ethyl complex 2c was not such an efficient initiator as the silylamido ones, but the alkoxy complex 4b gave an obviously faster and better controlled polymerization when compared to the zinc silylamido complexes.
ISSN	14779226
Issue Number	11
Volume Number	41
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-03-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Dioxanes Chemistry Organometallic Compounds Polymerization Zinc Aminophenols Catalysis Ligands Chemical Synthesis Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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