879286-78-9Relevant articles and documents
Alternating copolymerization of fluoroalkenes with carbon monoxide
Fujita, Tomoyuki,Nakano, Koji,Yamashita, Makoto,Nozaki, Kyoko
, p. 1968 - 1975 (2007/10/03)
The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH2= CH-CH2-CnF2n+1, with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH 2-CnF2n+1 group is the most electronegative substituent ever reported for the copolymerization (Taft's σ* value of 0.90 for CH2CF3). The copolymer obtained from CH 2=CH-CH2-C8F17 (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH2=CH- CH2-C4F9 (1b) was a pure polyspiroketal, as was revealed by infrared and 13C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the α-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.