5 years ago

Preparation and Characterization of Uranium–Iron Triple-Bonded UFe(CO)3− and OUFe(CO)3− Complexes

Preparation and Characterization of Uranium–Iron Triple-Bonded UFe(CO)3− and OUFe(CO)3− Complexes
Jia-Qi Wang, Chaoxian Chi, Mingbiao Luo, Mingfei Zhou, Wan-Lu Li, Jun Li, Hui Qu, Luyan Meng
We report the preparation of UFe(CO)3− and OUFe(CO)3− complexes using a laser-vaporization supersonic ion source in the gas phase. These compounds were mass-selected and characterized by infrared photodissociation spectroscopy and state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U 6d/5f and Fe 3d orbitals, featuring one covalent σ bond and two Fe-to-U dative π bonds in both complexes. The uranium and iron elements are found to exist in unique formal U(I or III) and Fe(−II) oxidation states, respectively. These findings suggest that there may exist a whole family of stable df–d multiple-bonded f-element-transition-metal compounds that have not been fully recognized to date. Iron loves U: Infrared photodissociation spectroscopy and quantum chemical calculations indicate that both UFe(CO)3− and OUFe(CO)3− complexes contain unprecedented uranium–iron triple bonds with one covalent σ bond and two Fe-to-U dative π bonds.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201703525

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