NDLI: Reactivity studies on [Cp′Fe(μ-I)]<sub>2</sub>: nitrido-, sulfido- and diselenide iron complexes derived from pseudohalide activation

Content Provider	Royal Society of Chemistry (RSC)
Author	Hohenberger, Johannes Daniliuc, Constantin G. Walter, Marc D. White, Peter S. Maron, Laurent Sutter, Jörg Jones, Peter G. Freytag, Matthias Reiners, Matthias Maekawa, Miyuki Meyer, Karsten
Copyright Year	2017
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.
Starting Page	4108
Ending Page	4122
Page Count	15
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c7sc00570a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Antiferromagnetism Carbodiimide Paramagnetism Isomeric shift Protein dimer Magnetic susceptibility X-ray crystallography Xylose Isotopes of iron Isocyanate Mössbauer spectroscopy Density functional theory NCO Metal nitrido complex Diamagnetism
Content Type	Text
Resource Type	Article
Subject	Chemistry

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