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Issue 25, 2016
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Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release

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Abstract

Here we present the syntheses and structural, spectroscopic, as well as electrochemical properties of four dinitrosyl iron complexes (DNICs) based on silicon- and carbon-derived di- and tripodal phosphines. Whereas CH3C(CH2PPh2)3 and Ph2Si(CH2PPh2)2 coordinate iron in a η2 – binding mode, CH3Si(CH2PPh2)3 undergoes cleavage of one Si–C bond to afford [Fe(NO)2(P(CH3)Ph2)2] at elevated temperatures. The complexes were characterized by IR spectroelectrochemistry as well as UV-vis measurements. The oxidized {Fe(NO)2}9 compounds were obtained by oxidation with (NH4)2[Ce(NO3)6] and their properties evaluated with Mössbauer and IR spectroscopy. Stability experiments on the complexes suggest that they are capable of releasing their NO-ligands in the oxidized {Fe(NO)2}9 but not in the reduced {Fe(NO)2}10 form. A detailed DFT analysis is provided in order to understand the electronic configurations and the complexes’ ability to release NO.

Graphical abstract: Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release

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Publication details

The article was received on 29 Mar 2016, accepted on 20 May 2016 and first published on 23 May 2016


Article type: Paper
DOI: 10.1039/C6DT01209D
Dalton Trans., 2016,45, 10271-10279

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    Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release

    F. Wittkamp, C. Nagel, P. Lauterjung, B. Mallick, U. Schatzschneider and U.-P. Apfel, Dalton Trans., 2016, 45, 10271
    DOI: 10.1039/C6DT01209D

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