%0 Journal Article
%A Rohde, Jan-Uwe
%A Betley, Theodore A.
%A Jackson, Timothy A.
%A Saouma, Caroline T.
%A Peters, Jonas C.
%A Que, Lawrence
%D 2007
%T XAS Characterization of a Nitridoiron(IV) Complex with a Very Short
Fe−N Bond
%U https://acs.figshare.com/articles/journal_contribution/XAS_Characterization_of_a_Nitridoiron_IV_Complex_with_a_Very_Short_Fe_N_Bond/2997889
%R 10.1021/ic700818q.s002
%2 https://acs.figshare.com/ndownloader/files/4698916
%K spectroscopic evidence
%K bond
%K π basicity
%K FeIV
%K metal coordination number
%K tetrahedral complexes
%K Fe
%K PhBPR
%K nitrido ligand
%K oxo ligand
%K XAS Characterization
%K interaction results
%X 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 FeI−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 [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 π basicity of the nitrido ligand than the oxo ligand and a lower metal coordination number for
the Fe(N) complex.
%I ACS Publications