A Series of Iron Nitrosyl Complexes {Fe–NO}6–9 and a Fleeting {Fe–NO}10 
Intermediate en Route to a Metalacyclic Iron Nitrosoalkane

Keilwerth, Martin; Hohenberger, Johannes; Heinemann, Frank W.; Sutter, Jörg; Scheurer, Andreas; Fang, Huayi; Bill, Eckhard; Neese, Frank; Ye, Shengfa; Meyer, Karsten

doi:10.1021/jacs.9b08053

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A Series of Iron Nitrosyl Complexes {Fe–NO}^6–9 and a Fleeting {Fe–NO}¹⁰ Intermediate en Route to a Metalacyclic Iron Nitrosoalkane

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Neese, Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Ye, Shengfa
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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引用

Keilwerth, M., Hohenberger, J., Heinemann, F. W., Sutter, J., Scheurer, A., Fang, H., Bill, E., Neese, F., Ye, S., & Meyer, K. (2019). A Series of Iron Nitrosyl Complexes {Fe–NO}^6–9 and a Fleeting {Fe–NO}¹⁰ Intermediate en Route to a Metalacyclic Iron Nitrosoalkane. Journal of the American Chemical Society, 141(43), 17217-17235. doi:10.1021/jacs.9b08053.

引用: https://hdl.handle.net/21.11116/0000-0005-4263-1

要旨

Iron–nitrosyls have fascinated chemists for a long time due to the noninnocent nature of the NO ligand that can exist in up to five different oxidation and spin states. Coordination to an open-shell iron center leads to complex electronic structures, which is the reason Enemark−Feltham introduced the {Fe–NO}ⁿ notation. In this work, we succeeded in characterizing a series of {Fe–NO}^6–9 complexes, including a reactive {Fe–NO}¹⁰ intermediate. All complexes were synthesized with the tris-N-heterocyclic carbene ligand tris[2-(3-mesitylimidazol-2-ylidene)ethyl]amine (TIMEN^Mes), which is known to support iron in high and low oxidation states. Reaction of NOBF₄ with [(TIMEN^Mes)Fe]²⁺ resulted in formation of the {Fe–NO}⁶ compound [(TIMEN^Mes)Fe(NO)(CH₃CN)](BF₄)₃ (1). Stepwise chemical reduction with Zn, Mg, and Na/Hg leads to the isostructural series of high-spin iron nitrosyl complexes {Fe–NO}^7,8,9 (2–4). Reduction of {Fe–NO}⁹ with Cs electride finally yields the highly reduced {Fe–NO}¹⁰ intermediate, key to formation of [Cs(crypt-222)][(TIMEN^Mes)Fe(NO)], (5) featuring a metalacyclic [Fe−(NO−NHC)³⁻] nitrosoalkane unit. All complexes were characterized by single-crystal XRD analyses, temperature and field-dependent SQUID magnetization methods, as well as ⁵⁷Fe Mössbauer, IR, UV/vis, multinuclear NMR, and dual-mode EPR spectroscopy. Spectroscopy-based DFT analyses provide insight into the electronic structures of all compounds and allowed assignments of oxidation states to iron and NO ligands. An alternative synthesis to the {Fe–NO}⁸ complex was found via oxygenation of the nitride complex [(TIMEN^Mes)Fe(N)](BF₄). Surprisingly, the resulting {Fe–NO}⁸ species is electronically and structural similar to the [(TIMEN^Mes)Fe(N)]⁺ precursor. Based on the structural and electronic similarities between this nitrosyl/nitride complex couple, we adopted the strategy, developed by Wieghardt et al., of extending the Enemark−Feltham nomenclature to nitrido complexes, rendering [(TIMEN^Mes)Fe(N)]⁺ as a {Fe–N}⁸ species.