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

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• 作者：Thomas R. Dugan ; Eckhard Bill ; K. Cory MacLeod ; Gemma J. Christian ; Ryan E. Cowley ; William W. Brennessel ; Shengfa Ye ; Frank Neese ; Patrick L. Holland
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：December 19, 2012
• 年：2012
• 卷：134
• 期：50
• 页码：20352-20364
• 全文大小：652K
• 年卷期：v.134,no.50(December 19, 2012)
• ISSN：1520-5126

文摘

This manuscript describes the formally iron(I) complexes L^MeFe(Py-R)₂ (L^Me = bulky 尾-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鈥揅 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鈥揅 bond formation in the dimer stores electrons from the formally reduced metal as a C鈥揅 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.