Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release
By Wittkamp, F.; Nagel, C.; Lauterjung, P.; Mallick, B.; Schatzschneider, U.; Apfel, U.-P.
Published in Dalton Trans
The Royal Society of Chemistry
2016
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 [small eta]2 - 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)29 compounds were obtained by oxidation with (NH4)2[Ce(NO3)6] and their properties evaluated with Mossbauer and IR spectroscopy. Stability experiments on the complexes suggest that they are capable of releasing their NO-ligands in the oxidized Fe(NO)29 but not in the reduced Fe(NO)210 form. A detailed DFT analysis is provided in order to understand the electronic configurations and the complexes
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