Synthesis and Hydrogenation of Bis(imino)pyridine Iron Imides

Suzanne C. Bart, Emil Lobkovsky, Eckhard Bill,† and Paul J. Chirik*
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, and Max-Plank Institute of Bioinorganic Chemistry, Stiftstrasse 34-36, D-45470 Mlheim an der Ruhr, Germany
J. Am. Chem. Soc., 2006, 128 (16), pp 5302–5303
DOI: 10.1021/ja057165y
Publication Date (Web): March 30, 2006
Copyright © 2006 American Chemical Society
†

 Max-Plank Institute of Bioinorganic Chemistry.

,
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, pc92@cornell.edu

Abstract

Abstract Image

Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3NCMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with Mössbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N−H bond formation as the rate-determining step in aniline formation.

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History

  • Published In Issue April 26, 2006
  • Received October 20, 2005

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