Secondary
Alkene Insertion and Precision Chain-Walking:
A New Route to Semicrystalline “Polyethylene” from α‑Olefins
by Combining Two Rare Catalytic Events
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Abstract
While
traditional polymerization of linear α-olefins (LAOs)
typically provides amorphous, low <i>T</i><sub>g</sub> polymers,
chain-straightening polymerization represents a route to semicrystalline
materials. A series of α-diimine nickel catalysts were tested
for the polymerization of various LAOs. Although known systems yielded
amorphous or low-melting polymers, the “sandwich” α-diimines <b>3</b>–<b>6</b> yielded semicrystalline “polyethylene”
comprised primarily of unbranched repeat units via a combination of
uncommon regioselective 2,1-insertion and precision chain-walking
events