Stereospecific Ring-Opening Metathesis Polymerization of Norbornene Catalyzed by Iron Complexes.

Developing well-defined iron-based catalysts for olefin metathesis would be a breakthrough achievement in the field not only to replace existing catalysts by inexpensive metals but also to attain a new reactivity taking advantage of the unique electronic structure of the base metals. Here, we present a two-coordinate homoleptic iron complex, Fe(HMTO)2 [HMTO=O-2,6-(2,4,6-Me3 C6 H2 )2 C6 H3 ], that is capable of performing ring-opening metathesis polymerization of norbornene to produce highly stereoregular polynorbornene (99 % cis, syndiotactic). The use of heteroleptic Fe(HMTO)(RO) [RO=(CH3 )2 CF3 CO, CH3 (CF3 )2 CO, or Ph(CF3 )2 CO] prepared in situ significantly increases the polymerization rate while preserving selectivity. The resulting polymers were characterized by 1 H and 13 C NMR spectroscopy and gel-permeation chromatography.