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.