Isolation of a Perfectly Linear Uranium(II) Metallocene
Guo, F.-S., Tsoureas, N., Huang, G.-Z., Tong, M.-L., Mansikkamäki, A., & Layfield, R. A. (2020). Isolation of a Perfectly Linear Uranium(II) Metallocene. Angewandte Chemie, 59(6), 2299-2303. https://doi.org/10.1002/anie.201912663
Published inAngewandte Chemie
© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
Reduction of the uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) with potassium graphite produces the "second-generation" uranocene [(eta(5)-(C5Pr5)-Pr-i)(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-6dz2 mixing.
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Additional information about fundingWe thank the ERC (CoG 646740), the EPSRC (EP/M022064/1), the NSF China (projects 21620102002, 21821003), the National Key Research and Development Program of China (2018YFA0306001), the Magnus Ehrnrooth Foundation, the CSC‐IT Center for Science in Finland, the Finnish Grid and Cloud Infrastructure (urn:nbn:fi:research‐infras‐2016072533), and Prof. H. M. Tuononen (University of Jyväskylä) for computational resources. ...
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