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Issue 33, 2011
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Subtle effects control the polymerisation mechanism in α-diimine iron catalysts

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Abstract

α-diimine iron complexes have been suggested to catalyse polymerisationvia two distinct pathways, depending on the spin state of the iron complex. Here, we study a typical complex of this family, R′′[N,N]FeCl2, with [N,N] = Cy–N[double bond, length as m-dash]CR′′–CR′′[double bond, length as m-dash]N–Cy (Cy = cyclohexyl, R′′ = PhF (para-fluorophenyl), PhOMe (para-methoxyphenyl), PhNMe2 (para-dimethylaminophenyl). With R′′ = PhF, PhOMe, polymerisation proceeds as a catalytic chain transfer (CCT) mechanism, with R′′ = PhNMe2, the polymerisation follows an atom transfer radical polymerisation (ATRP) pathway. Contrary to previous suggestions, we show that the spin-states of the complexes involved are not affected by the R′′ group. Instead, the different behaviour arises from a subtle interplay between the electron-withdrawing or donating character of the reasonably distant phenyl substituent and the iron centre, and small but crucial differences in the reorganisation energies affected during the reactions.

Graphical abstract: Subtle effects control the polymerisation mechanism in α-diimine iron catalysts

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Publication details

The article was received on 11 Jan 2011, accepted on 03 Jun 2011 and first published on 20 Jul 2011


Article type: Paper
DOI: 10.1039/C1DT10045A
Citation: Dalton Trans., 2011,40, 8419-8428
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    Subtle effects control the polymerisation mechanism in α-diimine iron catalysts

    M. P. Johansson and M. Swart, Dalton Trans., 2011, 40, 8419
    DOI: 10.1039/C1DT10045A

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