Organometallic polymers. XIV. Copolymerization of vinylcyclopentadienyl manganese tricarbonyl and vinylferrocene withN‐vinyl‐2‐pyrrolidone

N‐Vinyl‐2‐pyrrolidone(I) has been copolymerized with vinylferrocene(II) and vinylcyclopentadienyl manganese tricarbonyl(III) in degassed benzene solutions with the use of azobisisobutyronitrile (AIBN) as the initiator. The polymerizations proceed smoothly, and the relative reactivity ratios were determined asr1= 0.66,r2= 0.40 (for copolymerization of I with II, M1defined as II) andr1= 0.14 andr2= 0.09 (for copolymerization of I with III, M1defined as III). These copolymers were soluble in benzene, THF, chloroform, CCl4, and DMF. Molecular weights were determined by viscosity and gel‐permeation chromatography studies (universal calibration technique.) The copolymers exhibited values of M̄nbetween 5 × 103and 10 × 103and M̄wbetween 7 × 103and 17 × 103with M̄w/M̄n< 2. Upon heating to 260°C under N2, copolymers of III underwent gas evolution and weight loss. The weight loss was enhanced at 300°C, and the polymers became in creasingly insoluble. Copolymers of vinylferrocene were oxidized to polyferricinium salts upon treatment with dichlorodicyanoquinone (DDQ) oro‐chloranil (o‐CA) in benzene. Each unit of quinone incorporated into the polysalts had been reduced to its radical anion. The ratio of ferrocene to ferricinium units in the polysalts was determined. The polysalts did not melt at 360°C and were readily soluble only in DMF.