The alternating copolymerization of functional alkenes,
CH2CH(CH2)
x
OH
(x = 2, 3, 4, 9),
CH2CH(CH2)
x
COOH
(x = 1, 2, 4, 8), and 4-allylanisole, with carbon monoxide
was achieved by using
[Pd(Me-DUPHOS)(MeCN)2](BF4)2
[Me-DUPHOS = 1,2-bis(2,5-dimethylphospholano)benzene] as
the
catalyst. The resultant polymers were optically active with
isotactic sequences in the backbone. With
most alkenes, the polymers had poly(1,4-ketone) and/or
“regular” poly(spiroketal) (i.e.,
1,6-dioxaspiro[4.4]nonane) enchainments. However, with 4-penten-1-ol and
3-buten-1-ol, the participation of the pendant
hydroxyl group in intrachain reactions led to the formation of unusual
polycyclic repeating units in the
backbone. A comparison of
[Pd(Me-DUPHOS)(MeCN)2](BF4)2
with
[Pd(DPPP)(MeCN)2](BF4)2
[DPPP =
1,3-bis(diphenylphosphino)propane] indicated that the former
was a significantly better catalyst for the
alternating copolymerization of alkenols and alkenoic acids with carbon
monoxide.
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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