Dinitrogen Activation Upon Reduction of a Triiron(II) Complex

Abstract

Reaction of a trinuclear iron(II) complex, Fe3Br3L (1), with KC8 under N2 leads to dinitrogen activation products (2) from which Fe3(NH)3L (2‐1; L is a cyclophane bridged by three β‐diketiminate arms) was characterized by X‐ray crystallography. 1H NMR spectra of the protonolysis product of 2 synthesized under 14N2 and 15N2 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.

Catalytic Dinitrogen Fixation to Form Ammonia at Ambient Reaction Conditions Using Transition Metal-Dinitrogen Complexes

“…The bis(nitrido)‐bridged triiron‐dipotassium complex also serves as an isolable intermediate which can bind and liberate dinitrogen reversibly (Scheme ) 60. Similar cleavage of dinitrogen to form imido/amido‐bridged species using a triiron system has been reported where a stoichiometric amount of ammonia is obtained on further treatment with hydrogen chloride 65…”

Cobalt‐Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Reaction Conditions

“…However,t here are only limited examples of the catalytic conversion of N 2 into NH 3 . [1,2] In 2003, Schrock and Yandulov reported the first example of the catalytic formation of NH 3 from N 2 under ambient reactionc onditions using aM o À N 2 complex bearing at riamidoamine ligand. [3] In 2010, our group reported that N 2 -bridged Mo 2 ÀN 2 complexes bearing PNP-typep incerl igands worked as the most effective catalysts for the catalytic formation of NH 3 from N 2 .…”

A Tricopper(I) Complex Competent for O Atom Transfer, C–H Bond Activation, and Multiple O2 Activation Steps

“…[H­(DMF)]­[OTf] (DMF = dimethylformamide) was prepared as described previously . Deuterated 9,10-dihydroanthrancene ( d 4 -DHA), the ligand H 3 L, and tricopper complex 1 , were synthesized as reported previously. ,, …”