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• W1977944110 abstract "The α-diimine iron complexes R‘,R‘‘[N,N]FeCl2 (R‘,R‘‘[N,N] = R‘−NCR‘ ‘−CR‘ ‘N−R‘) are efficient catalysts for the atom-transfer radical polymerization (ATRP) of styrene when R‘ and R‘ ‘ are electron-donating substituents and favor catalytic chain transfer (CCT) when electron-withdrawing substituents are employed. An organometallic pathway, alongside a halogen-atom-transfer equilibrium, is proposed to mediate the observed reactivity. The model alkyl complexes, R‘,R‘‘[N,N]FeCl2(R), where R = PhCH2 and Ph(Me)CH, were generated via treatment of R‘,R‘‘[N,N]FeCl3 with RMgCl. The alkyl derivatives obtained from intermediate spin-state R‘,R‘‘[N,N]FeCl3 complexes were found to be stable to ca. −30 °C and favor CCT, whereas the alkyl derivatives derived from high-spin-state trichloride precursors are unstable above −78 °C and favor ATRP. Azo-initiated polymerizations of styrene are moderately controlled by α-diimine iron catalysts. The role of organometallic-mediated radical polymerization (OMRP) in the controlled polymerization of styrene is discussed: an analysis of the radical concentrations generated by the competing OMRP and ATRP equilibria indicates that the halogenophilicity of the Fe(II) catalyst dominates the carbophilic alkyl radical-trapping capacity of the Fe(II) species in this α-diimine catalyst system." @default.
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• W1977944110 date "2007-08-11" @default.
• W1977944110 modified "2023-09-23" @default.
• W1977944110 title "Organometallic Intermediates in the Controlled Radical Polymerization of Styrene by α-Diimine Iron Catalysts" @default.
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• W1977944110 doi "https://doi.org/10.1021/om700395h" @default.
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