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Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes [electronic resource].

Published:
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2017.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description:
pages 4,752-4,769 : digital, PDF file
Additional Creators:
Indiana University, Bloomington, United States. Department of Energy. Office of Basic Energy Sciences, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary:
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.
Report Numbers:
E 1.99:1348217
Subject(s):
Note:
Published through SciTech Connect.
04/05/2017.
Inorganic Chemistry 56 8 ISSN 0020-1669 AM
Bucinsky, Lukas; Breza, Martin; Lee, Wei-Tsung; Hickey, Anne; Dickie, Diane; Nieto, Ismael; DeGayner, Jordan; Harris, T.; Meyer, Karsten; Krzystek, J.; Ozarowski, Andrew; Nehrkorn, Joscha; Schnegg, Alexander; Holldack, Karsten; Herber, Rolfe; Telser, Joshua; Smith, Jeremy.
Funding Information:
FG02-08ER15996
CHE04-43580
DMR-1351959
DMR 1157490
NE 2064/1-1 FOR
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