Secondary alkene insertion and precision chain-walking: a new route to semicrystalline "polyethylene" from α-olefins by combining two rare catalytic events.
While traditional polymerization of linear α-olefins (LAOs) typically provides amorphous, low T(g) 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 3-6 yielded semicrystalline "polyethylene" comprised primarily of unbranched repeat units via a combination of uncommon regioselective 2,1-insertion and precision chain-walking events.
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
Tulaza
T
Vaidya
Kristine
K
Klimovica
Anne M
AM
LaPointe
Ivan
I
Keresztes
Emil B
EB
Lobkovsky
Olafs
O
Daugulis
Geoffrey W
GW
Coates
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D058105:Polymerization
D000475:Alkenes; D007097:Imines; D009942:Organometallic Compounds; D009532:Nickel