Protactinium and the intersection of actinide and transition metal chemistry.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 29434286.
- Also identified by DOI 10.1038/s41467-018-02972-z and PMC identifier 5809381.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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<sub>6</sub>(Pa<sub>4</sub>O(O<sub>2</sub>)<sub>6</sub>F<sub>12</sub>) [A = Rb, Cs, (CH<sub>3</sub>)<sub>4</sub>N], 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.