Bidentate Phenoxides as
Ideal Activating Ligands for
Living Ring-Opening Alkyne Metathesis Polymerization
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Abstract
We describe here a well-behaved initiator for ring-opening
alkyne
metathesis polymerization (ROAMP) of dibenzocyclooctynes. The reaction
produces living polymers with low polydispersities and predictable
molecular weights. We activate the well-known alkyne metathesis precatalyst,
[(N(<i>t</i>Bu)Ar)<sub>3</sub>MoCCH<sub>2</sub>CH<sub>3</sub>], with phenolic ligands that have σ-electron donating
substituents. We show that the chelating ability of these ligands
as well as the nature of the propagating molybdenum center have dramatic
effects on the outcome of the polymerization reaction