Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 45, Pages 14057-14060Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201707420
Keywords
ion spectroscopy; iron(V) nitride; photodissociation; photooxidation; spin crossover
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Funding
- European Research Council (ERC CoG) [682275]
- Czech Ministry of Education, Youth and Sports [LTAUSA17026]
- Czech Science Foundation [15-10279Y]
- COST action ECOSTBio
- Czech Academy of Sciences
- MINECO of Spain [CTQ2015-70795-P]
- Catalan DIUE of the Generalitat de Catalunya [2009SGR637]
- ICREA-Academia award
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The generation of iron(V) nitride complexes, which are targets of biomimetic chemistry, is reported. Temperature-dependent ion spectroscopy shows that this reaction is governed by the spin-state population of their iron(III) azide precursors and can be tuned by temperature. The complex [(MePy(2)TACN)Fe(N-3)](2+) (MePy(2)TACN-N-methyl-N, N-bis(2-picolyl)-1,4,7-triazacyclononane) exists as a mixture of sextet and doublet spin states at 300 K, whereas only the doublet state is populated at 3 K. Photofragmentation of the sextet state complex leads to the reduction of the iron center. The doublet state complex photodissociates to the desired iron(V) nitride complex. To generalize these findings, we show results for complexes with cyclam-based ligands.
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