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

Torres-Alacan, J., Krahe, O., Filippou, A. C., Neese, F., Schwarzer, D., & Voehringer, P. (2012). The photochemistry of [FeIIIN3(cyclam-ac)]PF6 at 266 nm. Chemistry-A European Journal, 18(10), 3043-3055. doi:10.1002/chem.201103294.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-000F-888C-C Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0027-C684-0
Genre: Journal Article

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Torres-Alacan, J., Author
Krahe, O., Author
Filippou, A. C., Author
Neese, F., Author
Schwarzer, D.1, Author              
Voehringer, P., Author
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1Research Group of Reaction Dynamics, MPI for biophysical chemistry, Max Planck Society, ou_578601              

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 Abstract: 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 Nα[BOND]Nβ bond, or to a photoreduced FeII species after Fe[BOND]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[BOND]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)]+ (2 red) 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)] (1 red) as a secondary product of the photochemical decomposition of 1. Molecular oxygen was further used to quench 1 red and 2 red to form what seems to be the elusive complex [Fe(O2)(cyclam-ac)]+ (6).

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Language(s): eng - English
 Dates: 2012-02-012012-03-05
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1002/chem.201103294
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Title: Chemistry-A European Journal
Source Genre: Journal
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Pages: - Volume / Issue: 18 (10) Sequence Number: - Start / End Page: 3043 - 3055 Identifier: -