Issue 33, 2011
From the journal:

Dalton Transactions

Subtle effects control the polymerisation mechanism in α-diimine iron catalysts†

Mikael P. Johansson*ab  and  Marcel Swart*ac  

* Corresponding authors

a Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, Spain

b Laboratory for Instruction in Swedish, Department of Chemistry, University of Helsinki, Helsinki, Finland

c Institució Catalana de Recerca i Estudis Avançats (ICREA), Barcelona, Spain
E-mail: mikael.johansson@iki.fi, marcel.swart@icrea.cat

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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Article information

DOI
https://doi.org/10.1039/C1DT10045A
Article type
Paper
Submitted
11 Jan 2011
Accepted
03 Jun 2011
First published
20 Jul 2011

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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