TY - JOUR
T1 - Palladium(II)-catalyzed alternating copolymerization of allene with carbon monoxide and the synthesis of terpolymer with alt-allene-carbon monoxide and alt-ethene-carbon monoxide blocks. Synthetic and mechanistic aspects
AU - Kacker, Smita
AU - Sen, Ayusman
PY - 1997
Y1 - 1997
N2 - The alternating copolymerization of 3,3-dimethylallene with carbon monoxide was achieved using [Pd(PPh3)2(MeCN)2](BF4)2 as the catalyst. The use of bidentate phosphines resulted in drastically reduced yields. In order to gain insight into the copolymerization mechanism, the stepwise successive insertions of 3,3-dimethylallene and carbon monoxide into palladium-carbon bonds in the complexes, Pd(PPh3)2(Me)(Cl), [Pd(PPh3)2(C(O)-C6H4-Me-p)(MeCN)](BF4), and [Pd[(Dppp)(Me)(MeCN)](BF4) (Dppp: 1,3-bis(diphenylphosphino)propane), were studied. These studies, in turn, led to a novel living catalytic system which was used to synthesize a terpolymer with alt-allene-carbon monoxide and alt-ethene-carbon monoxide blocks.
AB - The alternating copolymerization of 3,3-dimethylallene with carbon monoxide was achieved using [Pd(PPh3)2(MeCN)2](BF4)2 as the catalyst. The use of bidentate phosphines resulted in drastically reduced yields. In order to gain insight into the copolymerization mechanism, the stepwise successive insertions of 3,3-dimethylallene and carbon monoxide into palladium-carbon bonds in the complexes, Pd(PPh3)2(Me)(Cl), [Pd(PPh3)2(C(O)-C6H4-Me-p)(MeCN)](BF4), and [Pd[(Dppp)(Me)(MeCN)](BF4) (Dppp: 1,3-bis(diphenylphosphino)propane), were studied. These studies, in turn, led to a novel living catalytic system which was used to synthesize a terpolymer with alt-allene-carbon monoxide and alt-ethene-carbon monoxide blocks.
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U2 - 10.1021/ja9716620
DO - 10.1021/ja9716620
M3 - Article
AN - SCOPUS:0030723409
SN - 0002-7863
VL - 119
SP - 10028
EP - 10033
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 42
ER -