NDLI: Alkali aminoether-phenolate complexes: synthesis, structural characterization and evidence for an activated monomer ROP mechanism

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Sarazin, Yann Rosca, Sorin-claudiu Kozak, Christopher M. Dorcet, Vincent Rosca, Dragos-adrian Kerton, Francesca M. Carpentier, Jean-françois
Description	Author Affiliation: Rosca SC ( Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 263 avenue du Général Leclerc, 35042 Cedex, Rennes, France.)
Abstract	Several monometallic $\{LO^{i}\}M$ complexes of lithium (M = Li; i = 1 (1), 2 (2), 3 (3)) or potassium (M = K, i = 3 (4)) and the heteroleptic bimetallic lithium complex $\{LO^{3}\}Li·LiN(SiMe_{2}H)_{2}$ (5), all supported by monoanionic aminoether-phenolate $\{LO^{i}\}^{−}$ (i = 1–3) ligands , have been synthesized and structurally characterized. A large range of coordination motifs is represented in the solid state, depending on the chelating ability of the ligand , the size of the metal and the number of metallic centres found in the complex. Pulse-gradient spin-echo NMR showed that 1–4 are monomeric in solution, irrespective of their (mono- or di)nuclearity in the solid-state. VT $^{7}Li$ and DOSY NMR measurements conducted for 5 indicated that the two Li atoms in the complex do not exchange positions even at 80 °C. Upon addition of 1–10 equiv. of BnOH, the electron-rich and sterically congested $\{LO^{3}\}Li$ complex (3) promotes the controlled living and immortal ring-opening polymerisation of L-lactide. The combination of polymer end-group analyses and stoichiometric model reactions unambiguously provided evidence that ROP reactions catalyzed by these two-component $\{LO^{i}\}Li/BnOH$ catalyst systems operate according to an activated monomer mechanism, and not via the coordination–insertion scenario frequently assumed for similar alkali phenolate–alcohol systems.
ISSN	14779226
Issue Number	25
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-07-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Dioxanes Chemistry Ethers Metals, Alkali Organometallic Compounds Chemical Synthesis Phenols Models, Molecular Molecular Structure Polymerization Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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