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Title: XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe-N Bond

Abstract

X-ray absorption spectroscopy has been used to characterize the novel nitridoiron(IV) units in two [PhBP{sup R}{sub 3}]Fe(N) complexes (R = iPr and CyCH{sub 2}) and obtain direct spectroscopic evidence for a very short Fe-N distance. The distance of 1.51-1.55 {angstrom} reflects the presence of an Fe{triple_bond}N triple bond in accord with the observed Fe{triple_bond}N vibration observed for one of these species ({nu}{sub FeN} = 1034 cm{sup -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{sup I}-N{sub 2}-Fe{sup I}, Fe{sup II}-NPh{sub 2}, and Fe{sup III}NAd motifs, and those of recently described six-coordinate Fe{sup V}{triple_bond}N and Fe{sup VI}{triple_bond}N complexes. The observation that the Fe{sup IV}-N distances of two [PhBP{sup R}{sub 3}]Fe(N) complexes are shorter than the Fe{sup IV}-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.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
929893
Report Number(s):
BNL-80475-2008-JA
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US200822%%930
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 46; Journal Issue: 14
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IRON NITRIDES; IRON COMPLEXES; ABSORPTION SPECTROSCOPY; BOND LENGTHS; CHEMICAL BONDS; COORDINATION NUMBER; X-RAY SPECTROSCOPY; national synchrotron light source

Citation Formats

Rohde,J., Betley, T., Jackson, T., Saouma, C., Peters, J., and Que, Jr., L.. XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe-N Bond. United States: N. p., 2007. Web. doi:10.1021/ic700818q.
Rohde,J., Betley, T., Jackson, T., Saouma, C., Peters, J., & Que, Jr., L.. XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe-N Bond. United States. doi:10.1021/ic700818q.
Rohde,J., Betley, T., Jackson, T., Saouma, C., Peters, J., and Que, Jr., L.. Mon . "XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe-N Bond". United States. doi:10.1021/ic700818q.
@article{osti_929893,
title = {XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe-N Bond},
author = {Rohde,J. and Betley, T. and Jackson, T. and Saouma, C. and Peters, J. and Que, Jr., L.},
abstractNote = {X-ray absorption spectroscopy has been used to characterize the novel nitridoiron(IV) units in two [PhBP{sup R}{sub 3}]Fe(N) complexes (R = iPr and CyCH{sub 2}) and obtain direct spectroscopic evidence for a very short Fe-N distance. The distance of 1.51-1.55 {angstrom} reflects the presence of an Fe{triple_bond}N triple bond in accord with the observed Fe{triple_bond}N vibration observed for one of these species ({nu}{sub FeN} = 1034 cm{sup -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{sup I}-N{sub 2}-Fe{sup I}, Fe{sup II}-NPh{sub 2}, and Fe{sup III}NAd motifs, and those of recently described six-coordinate Fe{sup V}{triple_bond}N and Fe{sup VI}{triple_bond}N complexes. The observation that the Fe{sup IV}-N distances of two [PhBP{sup R}{sub 3}]Fe(N) complexes are shorter than the Fe{sup IV}-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.},
doi = {10.1021/ic700818q},
journal = {Inorganic Chemistry},
number = 14,
volume = 46,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}