Layfield_et_al-2019-Angewandte_Chemie_International_Edition.pdf (1.13 MB)
Isolation of a perfectly linear uranium(II) metallocene
journal contribution
posted on 2023-06-09, 19:37 authored by Fu-Sheng Guo, Nikolaos Tsoureas, Guo-Zhang Huang, Ming-Liang Tong, Akseli Mansikkamäki, Richard LayfieldRichard LayfieldReduction of the uranium(III) metallocene [(? 5 -C 5 i Pr 5 ) 2 UI] ( 1 ) with potassium graphite produces the 'second-generation' uranocene [(? 5 -C 5 i Pr 5 ) 2 U] ( 2 ), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f 3 6d 1 . Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2 , including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s-6d z 2 mixing.
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Publication status
- Published
File Version
- Accepted version
Journal
Angewandte Chemie International EditionISSN
1433-7851Publisher
WileyExternal DOI
Issue
6Volume
59Page range
1-5Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2019-11-13First Open Access (FOA) Date
2020-11-12First Compliant Deposit (FCD) Date
2019-11-13Usage metrics
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