- Treffer 1 von 1
Syntheses, Solid-state Structures and Catalytic Activity of Zinc Carboxylate Complexes in Lactide Polymerization
- Three dinuclear zinc carboxylate complexes [L1−3Zn(μ,η2-O2CPh)]2 (1, 2, 4) containing either the bidentate N,N′-chelating β-diketiminate ligand RNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L1, complex 1), the tridentate O,N,N-chelating ligand OC(Me)C(H)C(Me)NCH2CH2NMe2 (L2, complex 2) or the bis-N,N′-chelating bis-β-diketiminate ligand RNC(Me)C(H)C(Me)NNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L3, complex 4) were synthesized and characterized including single-crystal X-ray diffraction. Reaction of the neutral bis-β-diketimine (L3(H)2) with two equivalents of ZnMe2 leads to the expected heteroleptic dinuclear zinc complex L3(ZnMe)2 3 in 93 % yield. Further reaction with benzoic acid PhCO2H leads to complex 4. Complex 2 forms a rather strong carboxylate-bridged dimer, whereas the carboxylate groups in complexes 1 and 4 act as asymmetrical bridges between both Zn atoms, pointing to the formation of a weakly bonded dimer. The zinc atoms in 1 and 4 are tetrahedrally coordinated, whereas in 2 the coordination number is increased to five due to the coordination of the pendant donor arm. The ring opening polymerization (ROP) of rac-lactide was investigated with the zinc complexes 1–4 and diazabicycloundec-7-ene (DBU) as a co-catalyst. Complexes 2 and 3 are active polymerization catalysts, which in the presence of DBU converted 200 equiv. of rac-lactide into polylactide within 10 min at ambient temperature. The analysis of the crude polymer showed that the lactide polymerization with catalyst 2 occurs via a slightly modified activated-monomer mechanism.
Verfasserangaben: | Christoph Scheiper, Christoph Wölper, Dieter Bläser, Joachim Roll, Stephan Schulz |
---|---|
DOI: | https://doi.org/10.5560/ZNB.2014-4133 |
Titel des übergeordneten Werkes (Deutsch): | Zeitschrift für Naturforschung |
Dokumentart: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Datum der Veröffentlichung (online): | 30.10.2017 |
Jahr der Erstveröffentlichung: | 2014 |
Veröffentlichende Institution: | Westfälische Hochschule Gelsenkirchen Bocholt Recklinghausen |
Datum der Freischaltung: | 30.10.2017 |
Freies Schlagwort / Tag: | Carboxylate; N,N,O Ligands; N,N′ Ligands; Zinc |
Jahrgang: | 69b |
Erste Seite: | 1365 |
Letzte Seite: | 1374 |
Fachbereiche / Institute: | Fachbereiche / Wirtschaftsingenieurwesen |
Lizenz (Deutsch): | Es gilt das Urheberrechtsgesetz |