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DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032553.

Titanacyclobutane 221 exists in equilibrium with carbene 213, which catalyzes ring-opening metathesis polymerization of norbornene at 65°C to give a monodispersed polymer 234 (Mn=10400, Mw/Mn=1.13) via compound 233, (Scheme 112).[‌340‌] Thermolysis of 222 at 20°C in the presence of norbornene affords the trisubstituted titanacyclobutane 235, which also gives living polynorbornene 236 at 65°C (Mn=10450, Mw/Mn=1.09) (Scheme 112). The more highly substituted 235 is more reactive than 221 in the initiation reaction and thus affords a polymer with narrower polydispersity. The initiation efficiencies of 221 and 235 are the same and as high as 87%.

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