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Correlation of metal spin-state in alpha-diimine iron catalysts with polymerization mechanism
Laura E N Allan1, Michael P Shaver, Andrew J P White
1Contribution from the Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ, UK.
Abstract:
The alpha-diimine iron complexes, (R',R'')[N,N]FeCl(2) ((R',R'')[N,N] = R'-N=CR' '-CR' '=N-R', where R' = tert-butyl (tBu), cyclohexyl (Cy) and R' ' = phenyl (Ph), para-fluorophenyl (F-Ph), para-bromophenyl (Br-Ph), para-methylphenyl (Me-Ph), or para-methoxyphenyl (MeO-Ph)), are found to polymerize styrene through a catalytic chain transfer (CCT) mechanism. Magnetic moment measurements indicate that Fe(III) complexes containing these ligands possess intermediate (S = 3/2) spin-state iron centers. In contrast, Fe(III) complexes bearing proton (R' ' = H) and para-dimethylaminophenyl (R' ' = NMe(2)-Ph) substituents are high-spin and are efficient atom transfer radical polymerization (ATRP) catalysts. Hammett plots show a linear correlation of the substituent constant, sigma, with polymerization rate and polymer molecular weight, respectively.
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