Unwilling U-U bonding in U2@C80: cage-driven metal-metal bonds in di-uranium fullerenes

Physical Chemistry Chemical Physics : PCCP
Cina Foroutan-NejadMichal Straka

Abstract

Endohedral actinide fullerenes are rare and a little is known about their molecular properties. Here we characterize the U2@C80 system, which was recently detected experimentally by means of mass spectrometry (Akiyama et al., JACS, 2001, 123, 181). Theoretical calculations predict a stable endohedral system, (7)U2@C80, derived from the C80:7 IPR fullerene cage, with six unpaired electrons. Bonding analysis reveals a double ferromagnetic (one-electron-two-center) U-U bond at an rU-U distance of 3.9 Å. This bonding is realized mainly via U(5f) orbitals. The U-U interaction inside the cage is estimated to be about -18 kcal mol(-1). U-U bonding is further studied along the U2@Cn (n = 60, 70, 80, 84, 90) series and the U-U bonds are also identified in U2@C70 and U2@C84 systems at rU-U∼ 4 Å. It is found that the character of U-U bonding depends on the U-U distance, which is dictated by the cage type. A concept of unwilling metal-metal bonding is suggested: uranium atoms are strongly bound to the cage and carry a positive charge. Pushing the U(5f) electron density into the U-U bonding region reduces electrostatic repulsion between enclosed atoms, thus forcing U-U bonds.

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Citations

Feb 13, 2018·Chemistry : a European Journal·Adam JarosCina Foroutan-Nejad
Aug 29, 2018·Angewandte Chemie·Cina Foroutan-NejadGernot Frenking
Sep 21, 2018·Physical Chemistry Chemical Physics : PCCP·Therese Davis Della, Cherumuttathu H Suresh
Dec 31, 2019·Chemistry : a European Journal·Wangqiang ShenXing Lu
Jan 13, 2018·Physical Chemistry Chemical Physics : PCCP·Irene Casademont-ReigEduard Matito
Apr 23, 2021·Physical Chemistry Chemical Physics : PCCP·Xiao-Cheng XuHan-Shi Hu
Apr 24, 2021·Nature Communications·Jiaxin ZhuangNing Chen
Apr 5, 2017·The Journal of Physical Chemistry. a·Jakub KaminskýMichal Straka
Jan 30, 2018·Journal of the American Chemical Society·Xingxing ZhangNing Chen
Mar 3, 2020·Inorganic Chemistry·Xuanchu GeRuhong Zhou
Aug 24, 2021·Nature·Josef T BoronskiStephen T Liddle

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