Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen-transfer and oxygen-transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass-selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state.

Departament de Quimica and Institute of Computational Chemistry and Catalysis University of Girona Campus Montilivi Girona 17071 Spain

Department of Organic Chemistry Faculty of Science Charles University Prague Hlavova 2030 8 12843 Prague 2 Czech Republic

Serveis Tècnics de Recerca Universitat de Girona Parc Científic i Tecnològic 17003 Girona Spain

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