Reversible C-C bond formation between redox-active pyridine ligands in iron complexes.
作者： Patrick Holland , Frank Neese , Shengfa Ye , William Brennessel , Ryan Cowley
DOI: 10.1021/JA305679M
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摘要: This manuscript describes the formally iron(I) complexes LMeFe(Py-R)2 (LMe = bulky β-diketiminate; R H, 4-tBu), in which basal pyridine ligands preferentially accept significant unpaired spin density. Structural, spectroscopic, and computational studies on complex with 4-tert-butylpyridine (tBupy) indicate that S 3/2 species is a resonance hybrid between descriptions as (a) high-spin iron(II) antiferromagnetic coupling to anion radical (b) iron(I). When lacks protection of tert-butyl group, it rapidly reversibly undergoes reactions form new C–C bonds. In one reaction, coordinated couples triphenylmethyl radical, another, dimerizes give pyridine-derived dianion bridges two ions. The rapid, reversible bond formation dimer stores electrons from reduced metal ligands, demonstrated by using coupled diiron(II) gen...
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