ZnII Chlorido Complexes with Aliphatic, Chiral Bisguanidine Ligands as Catalysts in the Ring‐Opening Polymerisation of rac‐Lactide Using FT‐IR Spectroscopy in Bulk. Issue 47 (18th December 2017)

• Record Type: Journal Article
• Authors: Metz, Angela; McKeown, Paul; Esser, Bastian; Gohlke, Clara; Kröckert, Konstantin; Laurini, Larissa; Scheckenbach, Michael; McCormick, Strachan N.; Oswald, Michaela; Hoffmann, Alexander; Jones, Matthew D.; Herres‐Pawlis, Sonja
• Is Part Of: European journal of inorganic chemistry. Issue 47(2017)
• Page Start: 5557
• Page End: 5570
• Publication Date: 2017-12-18
• Subjects: Zinc -- Lactide -- Polymerisation -- N‐Donor -- X‐ray diffraction; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701147
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Eight new zinc complexes of bisguanidine ligands have been structurally characterised and tested for the polymerisation of lactide. Initially this necessitated the preparation of the new six bisguanidine ligands [TMG2 thf, DMEG2 thf, trans ‐TMG2 (1, 2)ch, trans ‐DMEG2 (1, 2)ch, R, R ‐TMG2 (1, 2)ch, R, R ‐DMEG2 (1, 2)ch]. With these ligands in hand, zinc chlorido complexes could be obtained, which were characterized by X‐ray crystallography and NMR spectroscopy. Furthermore, two new zinc chlorido complexes are reported, based on previous bisguanidine ligands [TMG2 (1, 3)ch, DMEG2 (1, 3)ch]. All complexes show a distorted tetrahedral coordination geometry. These eight complexes are utilised as catalysts in melt polymerization of unsublimed, technical rac ‐lactide at 150 °C. The most promising complexes were tested with different purities of lactide (technical and recrystallized) and with or without the addition of a co‐initiator. The conversion was determined using 1 H‐NMR or FT‐IR spectroscopy. Kinetic measurements show first‐order behaviour with respect to lactide. The end group of the polymer was determined by MALDI‐ToF measurements. Moreover, the impact of chiral complexes was examined with regard to the tacticity of the polymer. Complexes containing a thf backbone show the highest polymerisation activity with recrystallized rac ‐lactide and benzyl alcohol as co‐initiator. Abstract : The structural properties of eight new bisguanidine zinc chlorido complexes were investigated with X‐ray crystallography, DFT and natural bond orbital analysis calculations. A closer insight into the activity of lactide polymerisation (with variation of the lactide quality and addition of a co‐initiator) of these systems is presented. The reported complexes are the fastet robust N, N ‐guanidine zinc ROP catalysts reported so far.