Mechanism of carbene polymerisation revealed

26 April 2012

Scientists of the Van 't Hoff Institute for Molecular Sciences (HIMS) revealed the mechanism of rhodium catalyzed stereospecific ‘carbene’ polymerization reactions. These reactions allow the synthesis of new types of polymers. The results have been published in Angewandte Chemie International Edition (april 2012).

Scientists of the Van 't Hoff Institute for Molecular Sciences (HIMS) revealed the mechanism of rhodium catalyzed stereospecific ‘carbene’ polymerization reactions. These reactions allow the synthesis of new types of polymers.

These new stereoregular polymers are built from ‘carbene’ monomers ( :CHR) and have unusual properties (e.g. liquid crystalline) due to the fact that they have a polar group attached to every carbon atom of the polymeric chain.

The mechanism of these reactions was thus far unclear, but recently the scientists were able to unravel the mechanism in detail through a smart combination of catalysis screening and high resolution ESI-MS measurements. A remarkable observation was that the active species are easier formed from air-oxidized precursors than from non-oxidized precursors. These new insights make it possible to prepare ‘poly-carbenes’ in a much more efficient manner.

'Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species'
A. J. C. Walters, O. Troeppner, I. Ivanović-Burmazović, C. Tejel, M. P. del Río, J. N. H. Reek, B. de Bruin, Angewandte Chemie International Edition, 2012, DOI: 10.1002/anie.201200069

Published by  HIMS