The Photochemistry of [FeIIIN3(cyclam-ac)]PF6 at 266 nm

The photochemistry of iron azido complexes is quite challenging and poorly understood. For example, the photochemical decomposition of [FeIIIN3(cyclam-ac)]PF6 ([1]PF6), where cyclam-ac represents the 1,4,8,11-tetraazacyclotetradecane-1-acetate ligand, has been shown to be wavelength-dependent, leading either to the rare high-valent iron(V) nitrido complex [FeVN(cyclam-ac)]PF6 ([3]PF6) after cleavage of the azide N alpha- N beta bond, or to a photoreduced FeII species after Fe-Nazide bond homolysis. The mechanistic details of this intriguing reactivity have never been studied in detail. Here, the photochemistry of 1 in acetonitrile solution at room temperature has been investigated using step-scan and rapid-scan time-resolved Fourier transform infrared (FTIR) spectroscopy following a 266 nm, 10 ns pulsed laser excitation. Using carbon monoxide as a quencher for the primary iron-containing photochemical product, it is shown that 266 nm excitation of 1 results exclusively in the cleavage of the Fe?Nazide bond, as was suspected from earlier steady-state irradiation studies. In argon-purged solutions of [1]PF6, the solvent-stabilized complex cation [FeII(CH3CN)(cyclam-ac)]+ (2red) together with the azide radical (N3.) is formed with a relative yield of 80%, as evidenced by the appearance of their characteristic vibrational resonances. Strikingly, step-scan experiments with a higher time resolution reveal the formation of azide anions (N3-) during the first 500 ns after photolysis, with a yield of 20%. These azide ions can subsequently react thermally with 2?red to form [FeIIN3(cyclam-ac)] (1red) as a secondary product of the photochemical decomposition of 1. Molecular oxygen was further used to quench 1red and 2red to form what seems to be the elusive complex [Fe(O2)(cyclam-ac)]+ (6).