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Title: Protactinium and the intersection of actinide and transition metal chemistry

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, A 6Pa 4O(O 2) 6F 12 [A = Rb, Cs, (CH 3) 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.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Univ. de Lille, Lille (France). Physique des Lasers Atomes et Molecules
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1426227

Wilson, Richard E., De Sio, Stephanie, and Vallet, Valerie. Protactinium and the intersection of actinide and transition metal chemistry. United States: N. p., Web. doi:10.1038/s41467-018-02972-z.
Wilson, Richard E., De Sio, Stephanie, & Vallet, Valerie. Protactinium and the intersection of actinide and transition metal chemistry. United States. doi:10.1038/s41467-018-02972-z.
Wilson, Richard E., De Sio, Stephanie, and Vallet, Valerie. 2018. "Protactinium and the intersection of actinide and transition metal chemistry". United States. doi:10.1038/s41467-018-02972-z. https://www.osti.gov/servlets/purl/1426227.
@article{osti_1426227,
title = {Protactinium and the intersection of actinide and transition metal chemistry},
author = {Wilson, Richard E. and De Sio, Stephanie and Vallet, Valerie},
abstractNote = {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.},
doi = {10.1038/s41467-018-02972-z},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

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