XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe−N Bond

2007/06/15 by Jan‐Uwe Rohde, Theodore A. Betley, Timothy A. Jackson +3 · 5 citations
Chemistry · Materials Science · #Metal-Catalyzed Oxygenation Mechanisms #Lanthanide and Transition Metal Complexes #Magnetism in coordination complexes

paper · doi:10.1021/ic700818q

openalex publication_date 2007/06/15 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01

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 A reflects the presence of an FeN triple bond in accord with the observed FeN vibration observed for one of these species (nuFeN=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 FeI-N2-FeI, FeII-NPh2, and FeIIINAd motifs, and those of recently described six-coordinate FeVN and FeVIN complexes. The observation that the FeIV-N distances of two [PhBPR3]Fe(N) complexes are shorter than the FeIV-O bond lengths of oxoiron(IV) complexes may be rationalized on the basis of the greater pi basicity of the nitrido ligand than the oxo ligand and a lower metal coordination number for the Fe(N) complex.

Citations

• Density-functional approximation for the correlation energy of the inhomogeneous electron gas
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis

Cited by

• TERMINAL NITRIDO AND IMIDO COMPLEXES OF THE LATE TRANSITION METALS
• An Iron Nitride Complex
• Formation of Ammonia from an Iron Nitrido Complex
• An introduction to X-ray absorption spectroscopy and its in situ application to organometallic compounds and homogeneous catalysts
• High-valent iron [wikipedia]