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Issue 11, 2014
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Tuning ligand electronics and peripheral substitution on cobalt salen complexes: structure and polymerisation activity

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Abstract

A series of cobalt salen complexes, where salen represents an N2O2 bis-Schiff-base bis-phenolate framework, are prepared, characterised and investigated for reversible-termination organometallic mediated radical polymerisation (RT-OMRP). The salen ligands contain a cyclohexane diimine bridge and systematically altered para-substituted phenoxide moieties as a method to examine the electronic impact of the ligand on complex structure and reactivity. The complexes are characterised by single crystal X-ray diffraction, cyclic voltammetry, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and computational methods. Structural studies all support a tailorable metal centre reactivity altered by the electron-donating ability of the salen ligand. RT-OMRP of styrene, methyl methacrylate and vinyl acetate is reported and suggests that cobalt–carbon bond strength varies with the ligand substitution. Competing β-hydrogen abstraction affords long-chain olefin-terminated polymer chains and well controlled vinyl acetate polymerisations, contrasting with the lower temperature associative exchange mechanism of degenerative transfer OMRP.

Graphical abstract: Tuning ligand electronics and peripheral substitution on cobalt salen complexes: structure and polymerisation activity

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Publication details

The article was received on 09 Jul 2013, accepted on 09 Sep 2013 and first published on 09 Sep 2013


Article type: Paper
DOI: 10.1039/C3DT51846A
Citation: Dalton Trans., 2014,43, 4295-4304
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    Tuning ligand electronics and peripheral substitution on cobalt salen complexes: structure and polymerisation activity

    L. Chiang, L. E. N. Allan, J. Alcantara, M. C. P. Wang, T. Storr and M. P. Shaver, Dalton Trans., 2014, 43, 4295
    DOI: 10.1039/C3DT51846A

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