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Reactivity of an All-Ferrous Iron-Nitrogen Heterocubane under Reductive and Oxidative Conditions.

Chemistry (Weinheim an der Bergstrasse, Germany) (2015-09-17)
Crispin Lichtenberg, Demyan E Prokopchuk, Mario Adelhardt, Liliana Viciu, Karsten Meyer, Hansjörg Grützmacher
ABSTRACT

The reactivity of the all-ferrous FeN heterocubane [Fe4 (Ntrop)4 ] (1) with i) Brønsted acids, ii) σ-donors, iii) σ-donors/π-acceptors, and iv) one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(μ3 -imido) 48 electron complex in the former case and a tetranuclear all ferric μ-oxo-μ-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Tetrahydrofuran, anhydrous, ≥99.9%, inhibitor-free
Sigma-Aldrich
Tetrahydrofuran, anhydrous, contains 250 ppm BHT as inhibitor, ≥99.9%
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Tetrahydrofuran, contains 250 ppm BHT as inhibitor, ACS reagent, ≥99.0%
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TEMPO, 98%
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Tetrahydrofuran, contains 250 ppm BHT as inhibitor, puriss. p.a., ACS reagent, reag. Ph. Eur., ≥99.9%
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Tetrahydrofuran, suitable for HPLC, ≥99.9%, inhibitor-free
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Tetrahydrofuran, ReagentPlus®, ≥99.0%, contains 250 ppm BHT as inhibitor
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Trimethylphosphine, 97%
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TEMPO, purified by sublimation, 99%
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Trimethylphosphine solution, 1.0 M in THF
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Tetrahydrofuran, ACS reagent, ≥99.0%, contains 250 ppm BHT as inhibitor
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Tetrahydrofuran, contains 250 ppm BHT as inhibitor, ACS reagent, ≥99.0%
Sigma-Aldrich
Trimethylphosphine solution, 1.0 M in toluene