Dinitrogen Activation Upon Reduction of a Triiron(II) Complex

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 synthes...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-01, Vol.54 (5), p.1499-1503
Main Authors: Lee, Yousoon, Sloane, Forrest T., Blondin, Geneviève, Abboud, Khalil A., García-Serres, Ricardo, Murray, Leslie J.
Format: Article
Language:English
Subjects:
Activation
Ammonia
Atmospherics
Bridges (structures)
Chemical Physics
Chemical Sciences
Coordination chemistry
cyclophanes
dinitrogen activation
Infrared radiation
iron clusters
macrobicycles
Mossbauer spectroscopy
Physics
redox cooperativity
Reduction
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Summary: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. A trinuclear iron(II) complex, Fe3Br3L in which L is a cyclophane bridged by three β‐diketiminate arms, reacts with KC8 under a dinitrogen atmosphere to form complex Fe3(NH)3L among other products. Reactions with 14N2 and 15N2 confirm atmospheric N2 reduction, and ammonia was detected by the indophenol assay. IR and Mössbauer spectroscopy as well as elemental analysis support the assignment that the reduction product contains protonated N‐atom bridges.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201409676