Kinetics of Acyclic Diene Metathesis (ADMET) Polymerization. Influence of the Negative Neighboring Group Effect

摘要: The influence of the negative neighboring group has been quantified kinetically using hydrocarbon monomers containing oxygen and sulfur. Rate constants were determined for ADMET polymerization bis(4-pentenyl) ether (3), bis(5-hexenyl) (4), sulfide (5), (6) both Schrock's catalyst Mo(CHCMe2Ph)(N-2,6-C6H3-i-Pr2)(OCMe(CF3)2)2 [Mo] Grubbs' phenyl version ruthenium metathesis RuCl2(CHPh)(PCy3)2 [Ru]. Both catalysts experience effect functional presence. Further, a pure also demonstrated monomer 1,5-hexadiene. In this case, catalysis produces linear 1,4-polybutadiene in reaction that exhibits typical rate constant activation energy. On other hand, [Ru] leads principally to formation cyclic compounds rather than polymers. This change mechanism can be attributed multiple...