Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase

Erik Andris; Juraj Jašík; Laura Gómez; Miquel Costas; Jana Roithová

doi:10.1002/anie.201511374

Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase

Angew Chem Int Ed Engl. 2016 Mar 7;55(11):3637-41. doi: 10.1002/anie.201511374. Epub 2016 Feb 16.

Authors

Erik Andris¹, Juraj Jašík¹, Laura Gómez^{2

3}, Miquel Costas⁴, Jana Roithová⁵

Affiliations

¹ Department of Organic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 12843, Prague 2, Czech Republic.
² Departament de Quimica and Institute of Computational Chemistry and Catalysis (IQCC), University of Girona, Campus Montilivi, Girona, 17071, Spain.
³ Serveis Tècnics de Recerca (STR), Universitat de Girona, Parc Científic i Tecnològic, 17003, Girona, Spain.
⁴ Departament de Quimica and Institute of Computational Chemistry and Catalysis (IQCC), University of Girona, Campus Montilivi, Girona, 17071, Spain. miquel.costas@udg.edu.
⁵ Department of Organic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 12843, Prague 2, Czech Republic. roithova@natur.cuni.cz.

Abstract

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.

Keywords: C−H activation; IR spectroscopy; iron complexes; mass spectrometry; spin state.

Publication types

Research Support, Non-U.S. Gov't