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Title: Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations

Abstract

The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]+ complex, which has been characterized by M{umlt o}ssbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations. The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d3 system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe-N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe-N stretching frequency of an Fe(V)-nitrido complex and its Fe(III)-azide precursor. The NRVS data show a new isolated band at 864 cm-1 in the Fe(V)-nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)-N stretch. The calculated Fe-N stretching frequency is too high by {approx}75 cm-1. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm-1). The NRVS datamore » provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.« less

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
918003
Report Number(s):
SLAC-REPRINT-2007-210
Journal ID: ISSN 0002-7863; JACSAT; TRN: US200817%%929
DOE Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article
Journal Name:
J.Am.Chem.Soc.129:11053,2007
Additional Journal Information:
Journal Volume: 129; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; GROUND STATES; IRON COMPLEXES; MAGNETIC SUSCEPTIBILITY; SYNTHESIS; X-RAY SPECTROSCOPY; ABSORPTION SPECTROSCOPY; CHEMICAL BONDS; BOND LENGTHS; Other,OTHER

Citation Formats

Petrenko, T, George, S D, Aliaga-Alcalde, N, Bill, E, Mienert, B, Xiao, Y, Guo, Y, Sturhahn, W, Cramer, S P, Wieghardt, K, Neese, F, and /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley. Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations. United States: N. p., 2007. Web. doi:10.1021/ja070792y.
Petrenko, T, George, S D, Aliaga-Alcalde, N, Bill, E, Mienert, B, Xiao, Y, Guo, Y, Sturhahn, W, Cramer, S P, Wieghardt, K, Neese, F, & /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley. Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations. United States. https://doi.org/10.1021/ja070792y
Petrenko, T, George, S D, Aliaga-Alcalde, N, Bill, E, Mienert, B, Xiao, Y, Guo, Y, Sturhahn, W, Cramer, S P, Wieghardt, K, Neese, F, and /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley. 2007. "Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations". United States. https://doi.org/10.1021/ja070792y.
@article{osti_918003,
title = {Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations},
author = {Petrenko, T and George, S D and Aliaga-Alcalde, N and Bill, E and Mienert, B and Xiao, Y and Guo, Y and Sturhahn, W and Cramer, S P and Wieghardt, K and Neese, F and /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley},
abstractNote = {The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]+ complex, which has been characterized by M{umlt o}ssbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations. The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d3 system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe-N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe-N stretching frequency of an Fe(V)-nitrido complex and its Fe(III)-azide precursor. The NRVS data show a new isolated band at 864 cm-1 in the Fe(V)-nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)-N stretch. The calculated Fe-N stretching frequency is too high by {approx}75 cm-1. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm-1). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.},
doi = {10.1021/ja070792y},
url = {https://www.osti.gov/biblio/918003}, journal = {J.Am.Chem.Soc.129:11053,2007},
issn = {0002-7863},
number = ,
volume = 129,
place = {United States},
year = {Fri Oct 19 00:00:00 EDT 2007},
month = {Fri Oct 19 00:00:00 EDT 2007}
}