1980 Volume 37 Issue 10 Pages 677-684
Synthesis and chemical reaction of organometallic polymers containing 1, 3-diene-iron or 1, 3-dieneruthenium complexes in the side chain were investigated. Cationic polymerization of tricarbonyl (1-4-η-3-allyl-1, 3-pentadinen) iron with BF3OEt2 catalyst gave methanol insoluble polymer (the degree of polymerization, ca. 20). The monomer readily isomerized into tricarbonyl (1-4-η-3-propenyl-1, 3-pentadiene) iron by heating to 90°C and the resulting isomer was inert toward cationic polymerization. Cationic polymerization of (1-4-η-3 (2-vinyloxyethyl) -1, 3-pentadiene) tri (carbonyl) iron and the ruthenium analogue gave the corresponding polymers in high yields. Their molecular weights were 14, 000-21, 000. The diene-metal moiety in the polymer was successfully converted into the η3-allyl metal group by oxidative addition of hydrogen chloride at -70°C. The resulting polymer was treated with AgNO3, AgBF4, AgPF6 or tin-amalgam to form the metal-metal bond in the polymer molecule. The metal-metal bonding was detected based on the model reaction of binuclear bis (η3-allyl-metal) complex, [(1-3, 8-10) -η6-decadienylibis tri (carbonyl) iron] 2+, with silver ions or reducing agents, Zn or Sn etc. Organometallic polymer obtained by reaction of 1, 2-polybutadiene or 3, 4-polyisoprene with Fe (CO) 5 or Fe3 (CO) 12 partially contained (η4-diene) iron complex moiety in the main chain.
