The synthesis of precise polymer architectures that result from the regio- and stereoselective polymerization of monomers is a prerequisite for the synthesis of precision polymers. In order to be of significant benefit, the use of functional monomers is a must. This in turn requires polymerization systems and initiators, which allow for the precise polymerization of such monomers and which tolerate functional groups. Here, we report on the regio- and stereospecific ring opening metathesis polymerization (ROMP) of functional, strained olefins by novel, well-defined olefin metathesis catalysts predominantly based on molybdenum/tungsten imido and tungsten oxo alkylidene N-heterocyclic carbene (NHC) complexes. Via this approach, functional, (selectively hydrogenated) all-cis or all-transisotactic or syndiotactic (st) polymers and copolymers are accessible. Both, the prerequisites for and the influence of catalyst structure on either E- or Z-selectivity of polymerization, syndio- or isotacticity and functional group tolerance will be outlined. Also, selected examples of application will be presented.

Stereoselective ring-opening metathesis polymerization with chiral cationic molybdenum and tungsten imido/oxo/sulfido alkylidene N-heterocyclic carbene catalysts

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