"Probing the Tacticity of Ring-Opened Metathesis Polymers of Norbornene and Norbornadiene Diesters by NMR Spectroscopy"

Lionel Delaude, Albert Demonceau, and Alfred F. Noels

book cover 
           title: Novel Metathesis Chemistry: Well-Defined Initiator
                  Systems for Specialty Chemical Synthesis, Tailored
                  Polymers and Advanced Material Applications
          series: NATO Science Series II. Mathematics, Physics and Chemistry
          editor: Yavuz Imamoglu and Lajos Bencze
       publisher: Kluwer
            city: Dordrecht
            year: 2003
          volume: 122
      first page: 249
       last page: 261
            isbn: 978-1-4020-1570-0 (Print) 978-94-010-0066-6 (Online)
             doi: 10.1007/978-94-010-0066-6_21

Abstract: This chapter summarizes the various NMR experiments that were applied to probe the main stereochemical features of polymers prepared by ring-opening metathesis polymerization (ROMP) of 2,3-dicarboalkoxynorbornadienes and 2,3-dicarboalkoxynorbornenes catalyzed by the dichloro ruthenium arene dimer (RuCl2(p-cymene))2 in the presence of trimethylsilyldiazomethane (TMSD). Direct spectroscopic methods based on the examination of cross-coupling peaks in polymers derived from optically active monomers (1H COSY NMR) and indirect methods based on the analysis of the hydrogenated derivatives of unsaturated parent polyolefins (1H and 13C NMR) led to the same conclusion. They both showed that high trans, highly isotactic polymers were formed using the ruthenium-arene catalyst precursor.

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