XAS characterization of a nitridoiron(IV) complex with a very short Fe-N bond

Jan Uwe Rohde, Theodore A. Betley, Timothy A. Jackson, Caroline T. Saouma, Jonas C. Peters, Lawrence Que

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Abstract

X-ray absorption spectroscopy has been used to characterize the novel nitridoiron(IV) units in two [PhBPR3]Fe(N) complexes (R = iPr and CyCH2) and obtain direct spectroscopic evidence for a very short Fe-N distance. The distance of 1.51-1.55 Å reflects the presence of an Fe≡N triple bond in accord with the observed Fe≡N vibration observed for one of these species (νFeN = 1034 cm-1). This highly covalent bonding interaction results in the appearance of an unusually intense pre-edge peak, whose estimated area of 100(20) units is much larger than those of the related tetrahedral complexes with Fe I-N2-FeI, FeII-NPh2, and FeIII≡NAd motifs, and those of recently described six-coordinate FeV≡N and FeVI≡N complexes. The observation that the FeIV-N distances of two [PhBPR 3]Fe(N) complexes are shorter than the FeIV-O bond lengths of oxoiron(IV) complexes may be rationalized on the basis of the greater π basicity of the nitrido ligand than the oxo ligand and a lower metal coordination number for the Fe(N) complex.

Original languageEnglish (US)
Pages (from-to)5720-5726
Number of pages7
JournalInorganic chemistry
Volume46
Issue number14
DOIs
StatePublished - Jul 9 2007

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