End of Frustration: Catalytic Precision Polymerization with Highly Interacting Lewis Pairs.

Herein we report on the catalytic polymerization of diverse Michael-type monomers with high precision by using simple but highly active combinations of phosphorus-containing Lewis bases and organoaluminum compounds. The interacting Lewis pair catalysts enable the control of molecular weight and microstructure of the produced polymers. The reactions show a linear Mn vs consumption plot thus proving a living type polymerization. The initiation has been investigated by end-group analysis with ESI mass spectrometric analysis. With these main-group element Lewis acid base pairs, it is not only possible to polymerize sterically demanding, functionalized as well as heteroatom containing monomers but also, for the first time, to catalytically polymerize extended Michael systems, like 4-vinylpyridine.