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Title: Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes

Abstract

High-oxidation state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin state preferences of three-fold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(Im R) 3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(Im R) 3}Fe(NR')] +, R = Mes, R' = Ad (1- adamantyl, 3), tBu (4), have been investigated by electronic absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMEN Ar)FeN] +, (TIMEN Ar = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), have been investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (HFEPR) (for 3 and 4) and frequency-domain Fouriertransform (FD-FT) THz EPR (for 3), which reveal their zero-field splitting (zfs) parameters. Experimentally correlated theoretical studies comprising ligand-field theory (LFT) and quantum chemical theory (QCT), the latter including both density functional theorymore » (DFT) and ab initio methods reveal the key role played by the Fe3 d z2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin state preference of the complex. Lastly, the ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.« less

Authors:
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Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1348217
Grant/Contract Number:  
FG02-08ER15996; CHE04-43580; DMR-1351959; DMR 1157490; NE 2064/1-1 FOR
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 8; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bucinsky, Lukas, Breza, Martin, Lee, Wei-Tsung, Hickey, Anne K., Dickie, Diane A., Nieto, Ismael, DeGayner, Jordan A., Harris, T. David, Meyer, Karsten, Krzystek, J., Ozarowski, Andrew, Nehrkorn, Joscha, Schnegg, Alexander, Holldack, Karsten, Herber, Rolfe H., Telser, Joshua, and Smith, Jeremy M.. Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b00512.
Bucinsky, Lukas, Breza, Martin, Lee, Wei-Tsung, Hickey, Anne K., Dickie, Diane A., Nieto, Ismael, DeGayner, Jordan A., Harris, T. David, Meyer, Karsten, Krzystek, J., Ozarowski, Andrew, Nehrkorn, Joscha, Schnegg, Alexander, Holldack, Karsten, Herber, Rolfe H., Telser, Joshua, & Smith, Jeremy M.. Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes. United States. doi:10.1021/acs.inorgchem.7b00512.
Bucinsky, Lukas, Breza, Martin, Lee, Wei-Tsung, Hickey, Anne K., Dickie, Diane A., Nieto, Ismael, DeGayner, Jordan A., Harris, T. David, Meyer, Karsten, Krzystek, J., Ozarowski, Andrew, Nehrkorn, Joscha, Schnegg, Alexander, Holldack, Karsten, Herber, Rolfe H., Telser, Joshua, and Smith, Jeremy M.. Wed . "Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes". United States. doi:10.1021/acs.inorgchem.7b00512. https://www.osti.gov/servlets/purl/1348217.
@article{osti_1348217,
title = {Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes},
author = {Bucinsky, Lukas and Breza, Martin and Lee, Wei-Tsung and Hickey, Anne K. and Dickie, Diane A. and Nieto, Ismael and DeGayner, Jordan A. and Harris, T. David and Meyer, Karsten and Krzystek, J. and Ozarowski, Andrew and Nehrkorn, Joscha and Schnegg, Alexander and Holldack, Karsten and Herber, Rolfe H. and Telser, Joshua and Smith, Jeremy M.},
abstractNote = {High-oxidation state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin state preferences of three-fold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(ImR)3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(ImR)3}Fe(NR')]+, R = Mes, R' = Ad (1- adamantyl, 3), tBu (4), have been investigated by electronic absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMENAr)FeN]+, (TIMENAr = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), have been investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (HFEPR) (for 3 and 4) and frequency-domain Fouriertransform (FD-FT) THz EPR (for 3), which reveal their zero-field splitting (zfs) parameters. Experimentally correlated theoretical studies comprising ligand-field theory (LFT) and quantum chemical theory (QCT), the latter including both density functional theory (DFT) and ab initio methods reveal the key role played by the Fe3dz2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin state preference of the complex. Lastly, the ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.},
doi = {10.1021/acs.inorgchem.7b00512},
journal = {Inorganic Chemistry},
number = 8,
volume = 56,
place = {United States},
year = {Wed Apr 05 00:00:00 EDT 2017},
month = {Wed Apr 05 00:00:00 EDT 2017}
}

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