Organometallic polymers. XVI. Copolymerization of styrenetricarbonylchromium and the reaction of polystyrene with chromium hexacarbonyl

Styrenetricarbonylchromium (IV) has been synthesized. Monomer IV did not homopolymerize with free‐radical initiation but copolymerized with styrene, methyl acrylate, and vinylcymantrene. The copolymerizations were carried out in benzene solutions at 70°C with azobisisobutyronitrile as the initiator. The relative reactivity ratios were determined for the styrene and methyl acrylate copolymerizations. They were (defining M1 as monomer IV) r1 ≅ 0, r2 ≅ 1.39 for styrene copolymerizations and r1 ≅ 0, r2 ≅ 0.75 for methyl acrylate copolymerization. Polystyrene reacted with chromium‐hexacarbonyl in refluxing DME to produce a polymer in which about 32% of the benzene rings were complexed with Cr(CO)3 units. The use of a polystyrene of narrow molecular weight distribution in this reaction demonstrated that no decomposition of the polystyrene chains occurred.