Lake, Ben; Shaver, Michael. (2016). Data supporting "Iron(II) b-ketiminate complexes as mediators of controlled radical polymerisation" (2016) in Dalton Transactions - EPSRC EP/M000842/1, [dataset]. University of Edinburgh, School of Chemistry. https://doi.org/10.7488/ds/1406.
A series of tridentate, ONO- and ONN-chelating β-ketiminate ligands were synthesised via condensation
reactions, and complexed with iron(II) using [Fe(N(SiMe3)2)2THF]. The complexation reactions proceeded
in high yields to generate novel, monomeric, tetracoordinate iron(II) complexes, each bearing a bis(trimethylsilyl)
amide ligand, as confirmed by X-ray crystallography. These complexes were amenable to
further reaction (protonolysis) with alcohols and phenols, generating alkoxide/phenolate-containing
complexes that were dimeric in the solid state. All complexes synthesised were screened as potential
mediators of the controlled radical polymerisation (CRP) of styrene and methyl methacrylate under both
atom transfer radical polymerisation (ATRP) and organometallic mediated radical polymerisation (OMRP)
conditions. Whilst all of the complexes were relatively poor ATRP mediators under the conditions used here,
regardless of monomer choice, dispersities (Đ) as low as 1.58 for styrene and 1.23 for methyl methacylate
polymerisation under OMRP conditions could be achieved. The better performance in methacrylate polymerisation
suggests the formation of a stronger metal–carbon bond in these systems. In particular, the use
of a β-ketiminate ligand functionalised with an N,N-dimethylethylene pendant arm and a 2,6-diphenylphenolate
ligand affords a potential Fe-based mediator of methyl methacrylate OMRP.
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