Reversible C-C Bond Formation between Redox-Active Pyridine Ligands in Iron Complexes

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This article was originally published as:

Dugan, T., Bill. E., MacLeod, C., Christian, G., Cowley, R., Brennessel, W., Ye, S., Neese, F. & Holland, P. (2012). Reversible C-C bond formation between redox-active pyridine ligands in iron complexes. Journal of the American Chemical Society, 134(50), 20352-20364. doi:10.1021/ja305679m


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This manuscript describes the formally iron(I) complexes LMeFe(Py-R)2 (LMe = bulky β-diketiminate; R = H, 4-tBu), in which the basal pyridine ligands preferentially accept significant unpaired spin density. Structural, spectroscopic, and computational studies on the complex with 4-tert-butylpyridine (tBupy) indicate that the S = 3/2 species is a resonance hybrid between descriptions as (a) high-spin iron(II) with antiferromagnetic coupling to a pyridine anion radical and (b) high-spin iron(I). When the pyridine lacks the protection of the tert-butyl group, it rapidly and reversibly undergoes radical coupling reactions that form new C–C bonds. In one reaction, the coordinated pyridine couples to triphenylmethyl radical, and in another, it dimerizes to give a pyridine-derived dianion that bridges two iron(II) ions. The rapid, reversible C–C bond formation in the dimer stores electrons from the formally reduced metal as a C–C bond in the ligands, as demonstrated by using the coupled diiron(II) complex to generate products that are known to come from iron(I) precursors. [from publisher's website].


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At the time of writing Gemma Christian was at the University of Rochester