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Issue 5, 2017
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Reactivity studies on [Cp′Fe(μ-I)]2: nitrido-, sulfido- and diselenide iron complexes derived from pseudohalide activation

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Abstract

The iron half-sandwich [Cp′Fe(μ-I)]2 (Cp′ = 1,2,4-(Me3C)3C5H2, 1) reacts with the pseudohalides NCO, SCN, SeCN and N3 to give [Cp′Fe(μ-NCO)]2 (2), [Cp′Fe(μ-S)]2 (3), [Cp′Fe(μ-Se2)]2 (4) and [Cp′Fe(μ-N)]2 (5), respectively. Various spectroscopic techniques including X-ray diffraction, solid-state magnetic susceptibility studies and 57Fe Mössbauer spectroscopy were employed in the characterization of these species. Mössbauer spectroscopy shows a decreasing isomer shift with increasing formal oxidation state, ranging from Fe(II) to Fe(IV), in complexes 1 to 5. The sulfido-bridged dimer 3 exhibits strong antiferromagnetic coupling between the Fe(III) centers. This leads to temperature-independent paramagnetism (TIP) at low temperature, from which the energy gap between the ground and the excited state can be estimated to be 2J = ca. 700 cm−1. The iron(IV) nitrido complex [Cp′Fe(μ-N)]2 (5) shows no reactivity towards H2 (10 atm), but undergoes clean reactions with CO (5 bar) and XylNC (Xyl = 2,6-Me2C6H3) to form the diamagnetic isocyanate and carbodiimide complexes [Cp′Fe(CO)2(NCO)] (7) and [Cp′Fe(CNXyl)2(NCNXyl)] (8), respectively. All compounds were fully characterized, and density functional theory (DFT) computations provide useful insights into their formation and the electronic structures of complexes 3 and 5.

Graphical abstract: Reactivity studies on [Cp′Fe(μ-I)]2: nitrido-, sulfido- and diselenide iron complexes derived from pseudohalide activation

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Publication details

The article was received on 07 Feb 2017, accepted on 29 Mar 2017 and first published on 11 Apr 2017


Article type: Edge Article
DOI: 10.1039/C7SC00570A
Citation: Chem. Sci., 2017,8, 4108-4122
  • Open access: Creative Commons BY-NC license
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    Reactivity studies on [Cp′Fe(μ-I)]2: nitrido-, sulfido- and diselenide iron complexes derived from pseudohalide activation

    M. Reiners, M. Maekawa, C. G. Daniliuc, M. Freytag, P. G. Jones, P. S. White, J. Hohenberger, J. Sutter, K. Meyer, L. Maron and M. D. Walter, Chem. Sci., 2017, 8, 4108
    DOI: 10.1039/C7SC00570A

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