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

Chemical Science
Matthias ReinersMarc D Walter

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 ...Continue Reading

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Citations

Sep 8, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Jan RaederMarc D Walter
May 23, 2020·Angewandte Chemie·Shaoguang ZhangNeil C Tomson
Apr 11, 2017·Chemical Communications : Chem Comm·Matthias ReinersMarc D Walter
Jun 21, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthias ReinersMarc D Walter
Jul 1, 2020·Nature Chemistry·Matthias ReinersMarc D Walter
May 12, 2021·Chemical Reviews·Sebastian J K ForrestSven Schneider
Jun 16, 2021·Chemical Communications : Chem Comm·Luis M Aguirre QuintanaHenry S La Pierre
Nov 27, 2019·Inorganic Chemistry·Marius PetersMarc D Walter

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Methods Mentioned

BETA
X-ray
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Software Mentioned

JulX
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Gaussian
WinNormos for Igor Pro
SHELXL

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