Closed Shell Iron(IV) Oxo Complex with an Fe-O Triple Bond: Computational Design, Synthesis, and Reactivity.

ABSTRACT: Iron(IV)-oxo intermediates in nature contain two unpaired electrons in the Fe-O antibonding orbitals, which are thought to contribute to their high reactivity. To challenge this hypothesis, we designed and synthesized closed-shell singlet iron(IV) oxo complex [(quinisox)Fe(O)]⁺ (1⁺ ; quinisox-H=(N-(2-(2-isoxazoline-3-yl)phenyl)quinoline-8-carboxamide). We identified the quinisox ligand by DFT computational screening out of over 450 candidates. After the ligand synthesis, we detected 1⁺ in the gas phase and confirmed its spin state by visible and infrared photodissociation spectroscopy (IRPD). The Fe-O stretching frequency in 1⁺ is 960.5 cm^-1 , consistent with an Fe-O triple bond, which was also confirmed by multireference calculations.

SUBMITTER: Andris E 

PROVIDER: S-EPMC7756500 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature