Heterolepic β-Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Ghosh, Swarup;
GND
1198962429
Affiliation
Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany.
Schäfer, Pascal M.;
GND
1143264606
LSF
56218
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Dittrich, Dennis;
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Scheiper, Christoph;
GND
1166412016
LSF
57360
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Steiniger, Phillip;
Affiliation
Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany.
Fink, Gerhard;
ORCID
0000-0002-9024-3588
Affiliation
Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 52074 Aachen Germany.
Ksiazkiewicz, Agnieszka N;
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) NanoEnergieTechnikZentrum Carl-Benz-Str. 199 47057 Duisburg.
Tjaberings, Alexander;
GND
139931430
LSF
52177
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Wölper, Christoph;
GND
104362113X
LSF
58062
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) NanoEnergieTechnikZentrum Carl-Benz-Str. 199 47057 Duisburg.
Gröschel, André H.;
Affiliation
Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 52074 Aachen Germany.
Pich, Andrij;
ORCID
0000-0002-4354-4353
Affiliation
Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany.
Herres-Pawlis, Sonja;
GND
1205420940
ORCID
0000-0003-2896-4488
Affiliation
Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.
Schulz, Stephan

Zinc phenoxide complexes L1ZnOAr 14 (L1=Me2NC2H4NC(Me)CHC(Me)O) and L2ZnOAr 58 (L2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized β-ketoiminate ligands (L1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me2-C6H32, 6; 3,5-Me2-C6H33, 7; 4-Bu-C6H44, 8) with tuneable electronic and steric properties were synthesized and characterized. 18 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 18 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (Mn) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L–LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled 1H-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure.

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