Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA).
Angew Chem Int Ed Engl. 2015 Jan 26;54(5):1499-503. doi: 10.1002/anie.201409676. Epub 2014 Dec 11.
Reaction of a trinuclear iron(II) complex, Fe3 Br3 L (1), with KC8 under N2 leads to dinitrogen activation products (2) from which Fe3 (NH)3 L (2-1; L is a cyclophane bridged by three β-diketiminate arms) was characterized by X-ray crystallography. (1) H NMR spectra of the protonolysis product of 2 synthesized under (14) N2 and (15) N2 confirm atmospheric N2 reduction, and ammonia is detected by the indophenol assay (yield ∼30 %). IR and Mössbauer spectroscopy, and elemental analysis on 2 and 2-1 as well as the tri(amido)triiron(II) 3 and tri(methoxo)triiron 4 congeners support our assignment of the reduction product as containing protonated N-atom bridges.
三核铁(II)配合物 Fe3 Br3 L(1)与 KC8 在 N2 下反应,得到氮气活化产物(2),通过 X 射线晶体学对其进行了表征。(2)由 2 在(14)N2 和(15)N2 下合成的质子化产物的 1H NMR 谱证实了大气中 N2 的还原,并且通过吲哚酚测定法检测到氨(产率约为 30%)。IR 和 Mössbauer 光谱以及 2 和 2-1 以及三(酰胺)三铁(II) 3 和三(甲氧基)三铁 4 同系物的元素分析支持我们的结论,即还原产物含有质子化的 N 原子桥。