Polymers From Carbon Dioxide

We have reported a series of new bimetallic complexes as catalysts for the copolymerisation of carbon dioxide and cyclohexene oxide. These new catalysts are active at just 1 atmosphere pressure of carbon dioxide and show excellent turn-over-numbers and turn-over-frequencies. Indeed, some of the new catalysts have activities matching, and even exceeding, the best previously known catalysts but operate at a fraction of the carbon dioxide pressure (1/10 or 1/60 of the pressure).  We have reported the first examples of homogeneous Fe(III) and Mg(II) catalysts for this polymerization. The di-magnesium catalysts are particularly notable as they are highly active, yet the metal is abundant, inexpensive and colourless.   We have investigated, in significant detail, the polymerisation kinetics and have uncovered a rate law  and proposed a mechanism, which has been supported experimentally, spectroscopically and using DFT theory.  The catalysts are tolerant of excesses of chain transfer agents, including water; we have utilized this to prepare polymers where the end-groups can be controlled with very high selectivity.


  1. Kember, M. R.; Williams, C. K., J. Am. Chem. Soc. 2012, 134 , 15676
  2. Kember, M. R.; Jutz, F.; Buchard, A.; White, A. J. P.; Williams, C. K., Chem. Sci. 2012, 3 , 1245
  3. Kember, M. R.; Copley, J.; Buchard, A.; Williams, C. K., Polym. Chem. 2012, 3 , 1196
  4. Buchard, A.; Jutz, F.; Kember, M. R.; White, A. J. P.; Rzepa, H. S.; Williams, C. K., Macromolecules 2012, 45, 6781
  5. Kember, M. R.; Buchard, A.; Williams, C. K., Chem. Commun. 2011, 47 , 141
  6. Jutz, F.; Buchard, A.; Kember, M. R.; Fredrickson, S. B.; Williams, C. K., J. Am. Chem. Soc. 2011, 133, 17395
  7. Buchard, A.; Kember, M. R.; Sandeman, K. G.; Williams, C. K., Chem. Commun. 2011, 47, 212
  8. Kember, M. R.; White, A. J. P.; Williams, C. K. Macromolecules 2010, 43, 2291.
  9. Kember, M. R.; White, A. J. P.; Williams, C. K. Inorg. Chem. 2009, 48, 9535.
  10. Kember, M. R.; Knight, P. D.; Reung, P. T. R.; Williams, C. K. Angew. Chem. Int. Ed. 2009, 931.
  11. Williams, C. K.; Kember, M. R.; Knight, P. D., 20.10.2009, WO 2009/130470 A1