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Living and enantiomer-selective polymerization of allene initiated by Ni complex containing chiral phosphine
A new allylnickel(II) complex ([S(R)]-N-[(1S)-2-(diphenylphosphino)-1-phenylethyl]-2-methyl-2-propanesulfinamide)?(2,?2,?2-?trifluoroacetato-?kappaO)?(pi-allyl)?nickel (2) was designed and prepared by using chiral phosphine. 2 was revealed to efficiently initiate the polymerization of L- and D-N-(1-(dodecylamino)-1-oxopropan-2-yl)-4-(propa-1,2-dien-1-yloxy)-benzamide (L-1 and D-1) in a living/controlled chain growth manner. Polymerization kinetics of L-1 and D-1 indicated that L-1 preferentially polymerized over the antipode D-1 by a factor of 1.9. In block copolymerization of rac-1 using the poly-L-150 as the macroinitiator, the polymerization proceeded in enantiomer-selective manner. It was found that enantiomeric excess (ee) value of the recovered monomer increased with the monomer conversion and finally reached to the maximum of 34%. These results suggest this chiral phosphine complex exhibits enantiomer-selectivity for the polymerization of chiral allene derivative monomer.
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Reference£º
Pyridazine – Wikipedia,
Pyridazine | C4H4N2776 – PubChem