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- W2086347560 abstract "A π-allylrhodium complex, Rh[η3-CH(Ar)C{C(CHAr)CH2C(CHAr)CH2CH2CHCHAr}CH2](PPh3)2 (Ar = C6H4OMe-p) (1), catalyzes alternating copolymerization of arylallenes (phenylallene, (4-methylphenyl)allene, (4-methoxyphenyl)allene, (4-chlorophenyl)allene, (4-fluorophenyl)allene, (4-butylphenyl)allene, and (4-tert-butylphenyl)allene) with carbon monoxide (1 atm) at room temperature to give the corresponding polyketones, I−[−CO−C(CHAr)CH2−]n (I = CH2C(CHAr)C(CHAr)CH2C(CHAr)CH2CH2CHCHAr, where Ar = C6H4OMe-p). The polymers contain the 2,3-polymerized arylallene unit rather than the 1,2-polymerized unit. The CC double bond in the repeating unit has a Z configuration, which is confirmed by the 1H NMR spectrum using ROESY technique. The living polymerization is demonstrated by (1) the 1H NMR spectrum of the polymers showing signals of the terminal group I originally contained in 1, (2) an increase in molecular weight (Mn) of the polymer with narrow polydispersity throughout the polymerization, and (3) a linear relationship between the molecular weight and the monomer-to-catalyst ratio. Copolymerization of phenylallene with carbon monoxide catalyzed by 1 and subsequent addition of (4-methoxyphenyl)allene to the reaction mixture afford the block copolyketone I−[{−CO−C(CHPh)−CH2−}m−{CO−C(CH−C6H4OMe-p)−CH2−}n], while copolymerization of an equimolar mixture of phenylallene and (4-methoxyphenyl)allene with carbon monoxide gives the random copolyketone I−{−CO−C(CHPh)−CH2−/−CO−C(CHC6H4OMe-p)−CH2−}n. These two copolyketones are characterized by comparison of the 13C{1H} NMR spectra." @default.
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- W2086347560 date "1998-11-13" @default.
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- W2086347560 title "Alternating Copolymerization of Arylallenes with Carbon Monoxide Catalyzed by a π-Allylrhodium Complex. Synthesis of New Polyketones with Regulated Structure and Molecular Weight" @default.
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