The capability of some -heterocyclic carbenes (NHCs) to reversibly dimerize is exploited to access dynamic polymer networks. Benzimidazolium motifs serving as NHC precursors have thus been supported onto copolymer chains by reversible addition-fragmentation chain transfer (RAFT) copolymerization of styrene and up to 20 mol % of 4-vinylbenzyl-ethyl-benzimidazolium chloride. Molecular versions of 1,3-dialkyl benzimidazolium salts have been synthesized as models, the deprotonation of which with a strong base yields the NHC dimers in the form of tetraaminoalkenes.
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