Sustainable Polymerization Catalysis for Advanced Biorenewable Polymeric Materials

• Applicant: Professor Dr. Jun Okuda
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2014 to 2017
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 246488333

• Final Report Year: 2017

Final Report Abstract

Control of activity and stereoselectivity during ring-opening polymerization of lactide as the premier biorenewable monomer remains a challenge. Molecularly defined initiators systems based on earth-abundant metals were developed containing easily accessible ligand frameworks. Using an OSSO-type bis(phenolate) ligand incorporating a 1,1’-ferrocenyl backbone redox-switchability during RÒP of lactide was observed. A series of hydridotriphenylborates of group 1 and 2 as well as zinc and aluminum was shown to exhibit a remarkable high activity toward hydroboration of carbonyl substrates and toward ring-opening polymerization of lactide. As potentially active ROP initiators a new series of alkaline earth metal amides has been synthesized.

Publications

• Alkali Metal Hydridotriphenylborates [(L)M][HBPh3] (M = Li, Na, K): Chemoselective Catalysts for Carbonyl and CO2 Hydroboration. J. Am. Chem. Soc. 2016, 138, 10790–1079
  Mukherjee, D.; Osseili, H.; Spaniol, T. P.; Okuda, J.
  (See online at https://doi.org/10.1021/jacs.6b06319)
• Lanthanum Complexes Containing a Bis(phenolate) Ligand with a Ferrocene-1,1’- diyldithio Backbone: Synthesis, Characterization, and Ring-opening Polymerization of rac-Lactide. Dalton Trans. 2016, 45, 8127–8133
  Hermans, C.; Rong, W.; Spaniol, T. P.; Okuda, J.
  (See online at https://doi.org/10.1039/c6dt00272b)
• Magnesium Hydridotriphenylborate [Mg(thf)6][HBPh3]2: A Versatile Hydroboration Catalyst. Chem. Commun. 2016, 52, 13155–13158
  Mukherjee, D.; Shirase, S.; Mashima, K.; Okuda, J.
  (See online at https://doi.org/10.1039/c6cc06805g)
• Ring-Opening of Cyclic Ethers by Aluminum Hydridotriphenylborate. Chem. Commun. 2017
  Mukherjee, D.; Osseili, H.; Truong, K.-N.; Spaniol, T. P.; Okuda, J.
  (See online at https://doi.org/10.1039/c7cc01159h)