Correlation of metal spin-state in α-diimine iron catalysts with polymerization mechanism

被引：58
作者：
Allan, Laura E. N. [1 ]
Shaver, Michael P. [1 ]
White, Andrew J. P. [1 ]
Gibson, Vernon C. [1 ]
机构：
[1] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AZ, England
来源：
INORGANIC CHEMISTRY | 2007年 / 46卷 / 21期
关键词：
D O I：
10.1021/ic701500y
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The alpha-diimine iron complexes, (R',R '')[N,N]FeCl2 ((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 paradimethylaminophenyl (R '' = NMe2-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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页码：8963 / 8970
页数：8
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