Protactinium and the intersection of actinide and transition metal chemistry

Wilson, Richard E.; De Sio, Stephanie; Vallet, Valerie

doi:10.1038/s41467-018-02972-z

Protactinium and the intersection of actinide and transition metal chemistry

Journal Article · Mon Feb 12 00:00:00 EST 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-02972-z· OSTI ID:1426227

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Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Univ. de Lille, Lille (France). Physique des Lasers Atomes et Molecules

The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A₆Pa₄O(O₂)₆F₁₂ [A = Rb, Cs, (CH₃)₄N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1426227

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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