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

Bucinsky L, Breza M, Lee WT, Hickey AK, Dickie DA, Nieto I, Degayner JA, Harris TD, Meyer K, Krzystek J, Ozarowski A, Nehrkorn J, Schnegg A, Holldack K, Herber RH, Telser J, Smith JM (2017)

Publication Type: Journal article

Publication year: 2017

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 56

Pages Range: 4751-4768

Journal Issue: 8

DOI: 10.1021/acs.inorgchem.7b00512

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 threefold 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′ = 1-adamantyl (3), ^tBu (4), were 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), were 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 (for 3 and 4) and frequency-domain Fourier-transform (FD-FT) terahertz electron paramagnetic resonance (for 3), which reveal their zero-field splitting parameters. Experimentally correlated theoretical studies comprising ligand-field theory and quantum chemical theory, the latter including both density functional theory and ab initio methods, reveal the key role played by the Fe 3dz² (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin-state preference of the complex. 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.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Slovak University of Technology in Bratislava / Slovenská Technická Univerzita v Bratislave (STU)

Slovakia (SK) Indiana University

United States (USA) (US) University of New Mexico (UNM) / Universidad de Nuevo México

United States (USA) (US) New Mexico State University (NMSU)

United States (USA) (US) Northwestern University

United States (USA) (US) Florida State University (FSU)

United States (USA) (US) University of Washington

United States (USA) (US) Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)

Germany (DE) Hebrew University of Jerusalem

Israel (IL) Roosevelt University

United States (USA) (US)

How to cite

APA:

Bucinsky, L., Breza, M., Lee, W.-T., Hickey, A.K., Dickie, D.A., Nieto, I.,... Smith, J.M. (2017). Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes. Inorganic Chemistry, 56(8), 4751-4768. https://doi.org/10.1021/acs.inorgchem.7b00512

MLA:

Bucinsky, Lukas, et al. "Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes." Inorganic Chemistry 56.8 (2017): 4751-4768.

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