摘要
A new allylnickel(II) complex([S(R)]-N-[(1 S)-2-(diphenylphosphino)-1-phenylethyl]-2-methyl-2-propanesulfinamide)(2,2,2-trifluoroacetato-k O)(p-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.
A new allylnickel(II) complex([S(R)]-N-[(1 S)-2-(diphenylphosphino)-1-phenylethyl]-2-methyl-2-propanesulfinamide)(2,2,2-trifluoroacetato-k O)(p-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.
基金
sponsored by the National Natural Science Foundation of China(Nos.21622402,51673057,and 21574036)
the Thousand Young Talents Program of China and the Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.sklssm201624)for Financial Support
