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

X-ray absorption spectroscopy has been used to characterize the novel nitridoiron(IV) units in two [PhBP^R_3]Fe(N) complexes (R = iPr and CyCH_2) 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 Fe_≡N vibration observed for one of these species (ν_(FeN) = 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−N_2−Fe^I, Fe^(II)−NPh_2, and Fe^(III)_≡NAd motifs, and those of recently described six-coordinate Fe^V≡N and Fe^V≡IN complexes. The observation that the Fe^(IV)−N distances of two [PhBPR_3]Fe(N) complexes are shorter than the Fe^(IV)−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.