Polyamine-Stabilized Sodium Aryloxides: Simple Initiators for the Ring-Opening Polymerization of rac-Lactide
Metalation of 2,4,6-tri(methyl)phenol (MeArOH) and 2,6-di(tert-butyl)-4-methylphenol (BuArOH) with NaN(SiMe3)2 in toluene and in the presence of stoichiometric amounts of the polydentate amines N,N,N′,N′-tetramethylethylenediamine (TMEDA) and N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) aff...
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Published in | Inorganic chemistry Vol. 50; no. 8; pp. 3589 - 3595 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
18.04.2011
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Subjects | |
Online Access | Get full text |
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Summary: | Metalation of 2,4,6-tri(methyl)phenol (MeArOH) and 2,6-di(tert-butyl)-4-methylphenol (BuArOH) with NaN(SiMe3)2 in toluene and in the presence of stoichiometric amounts of the polydentate amines N,N,N′,N′-tetramethylethylenediamine (TMEDA) and N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) affords three new sodium aryloxide complexes [Na(μ-OArBu)(TMEDA)]2 (3), [Na(μ-OArMe)(PMDETA)]2 (4), and [Na(OArBu)(PMDETA)] (5). Complexes 3 to 5 have been isolated as crystalline materials in reasonable yields and characterized in the solid state by X-ray crystallography and in solution by NMR spectroscopy. Complexes 3 to 5 and the related [tris(2-dimethylaminoethyl)amine] (Me6TREN) derivatives [Na(OArMe)(HOArMe)(Me6TREN)] (1) and [Na(OArBu)(Me6TREN)] (2), recently prepared in our group, are shown to be active as initiators for the ring-opening polymerization (ROP) of rac-lactide with benzyl alcohol as a co-initiator. However, during the course of the polymerization reactions intrachain and stereorandom transesterification side-reactions were observed under some of the experimental conditions tested. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic102542q |