Azoimido ligands (M≡Nγ-Nβ=NαR) are typically unstable and expel dinitrogen to generate metal imido complexes. The primary applications of metal complexes containing azoimido ligands have been studying the dinitrogen extrusion and nitrene transfer mechanisms. The thermal instability of these ligands hampers their use as ancillary ligands in catalytic metal complexes. Tethered tungsten-alkylidene complexes bearing azoimido ligands are synthesized, characterized, and tested as initiators for ring expansion metathesis polymerization (REMP). In this work tethered alkylidene complexes bearing azoimido ligands are stable enough to be REMP initiators. Moreover, the azoimido initiators are more efficient and stereoselective than the corresponding alkyl/aryl imido derivatives (M≡NR).

REMP catalysts with unusual ancillary ligands

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