title: Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release.
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 η(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)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.
authors.affiliation: Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: F
authors.initials: F
authors.lastname: Wittkamp
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany. ulrich.schatzschneider@uni-wuerzburg.de.
authors.forename: C
authors.initials: C
authors.lastname: Nagel
authors.affiliation: Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: P
authors.initials: P
authors.lastname: Lauterjung
authors.affiliation: Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: B
authors.initials: B
authors.lastname: Mallick
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany. ulrich.schatzschneider@uni-wuerzburg.de.
authors.forename: U
authors.initials: U
authors.lastname: Schatzschneider
authors.affiliation: Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
authors.forename: U-P
authors.initials: UP
authors.lastname: Apfel