Abstract
Coordination polymerizations of (trimethylsilylmethyl)allene 1 and (t-butyldimethylsilyloxy)allene 2 were performed by use of [(π-allyl)NiX]2 as the initiator. The living polymerization was achieved with [(π-allyl)NiBr]2 by the aid of additive ligand, Ph3As for 1 and Ph3P or (PhO)3P for 2. The polymers produced from 1 mainly (>95%) consisted of the 2,3-polymerization unit having the allylsilane structure. In the polymerization of 2, the polymer produced in the absence of the phosphine ligands exclusively consisted of the 2,3-polymerization unit having the silyl enol ether group, while, in the presence of them, the 1,2-po]ymerization unit was partly involved.
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The concentration of nickel was determined by the chelate titration. The supernatant (5 ml) of the toluene solution of Ni(COD)2 was evaporated to dryness. The residue was dissolved in 1 M HCl aq. and neutralized with NH3 aq. The resulting solution was diluted with water in a 50 ml volumetric flask and titrated three times by 0.01 M EDTA-2Na aq. in the presence of murexide as the indicator.
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Suzuki, M., Takao, T., Sakamoto, N. et al. Ni-Catalyzed Living Coordination Polymerization of Allenes Having Si-Based Functional Groups. Polym J 31, 1021–1024 (1999). https://doi.org/10.1295/polymj.31.1021
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DOI: https://doi.org/10.1295/polymj.31.1021