title: Photolysis of a High-Spin Azidoiron(III) Complex Studied by Time-Resolved Fourier-Transform Infrared Spectroscopy.
abstract: The laser-flash photolysis of the high-spin azidoiron(III) complex [FeIII(Me3Cyclam-ac)(N3)]PF6([1]PF6) in liquid acetonitrile solution at room temperature was explored by time-resolved Fourier-transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam-ac)(NCCH3)]+([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal-containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen-containing fragment was quenched with iodide to form azide anions. In the presence of N3-, the photoreduction created the elusive hexanitrogen radical anion N6.-as a transient byproduct.
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität, Wegelerstraße 12, 53117, Bonn, Germany.
authors.forename: Joel
authors.initials: J
authors.lastname: Torres-Alacan
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität, Wegelerstraße 12, 53117, Bonn, Germany.
authors.forename: Peter
authors.identifier: http://orcid.org/0000-0003-3098-0428
authors.initials: P
authors.lastname: Vöhringer
keywords: high-valent iron; infrared spectroscopy; photochemistry; time-resolved; transition-metal complexes