"Controlled Radical Polymerization of Vinyl Monomers Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes"

Sébastien Delfosse, Aurore Richel, Lionel Delaude, Albert Demonceau, and Alfred F. Noels

book cover 
           title: Controlled/Living Radical Polymerization. From Synthesis to Materials
          series: ACS Symposium Series
          editor: Krysztof Matyjaszewski
       publisher: American Chemical Society
            city: Washington, DC
            year: 2006
          volume: 944
      first page: 40
       last page: 55
            isbn: 0-8412-3991-6
             doi: 10.1021/bk-2006-0944.ch004

Abstract: The relative catalytic activities of a series of ruthenium-based complexes of the general formula [RuCl2(p-cymene)(NHC)], [RuCl2(=CHPh)(PR3)(NHC)], and [RuCl2(=CHPh)(NHC)2] (NHC is a N-heterocyclic carbene ligand) were determined by investigating the atom transfer radical polymerization (ATRP) of methyl methacrylate and styrene. The catalytic activity of a variety of related [RuCl(O^N)(=CHR)(NHC)] complexes and of their cationic counterparts, [Ru(O^N)(=CHR)(NHC)]+ BF4- (R = Ph or OEt, O^N is a Schiff base ligand), is also reported. The results clearly demonstrate that, with both methyl methacrylate and styrene, subtle modifications of the substituents of the NHC ligand lead to dramatic changes in the ability of the resulting ruthenium complexes to favor the occurrence of a well-behaved ATRP.

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