Third-highest oxidation state secures rhodium a place on the podium

For the first time, a team has detected rhodium in the +7 oxidation state, the third highest oxidation state experimentally among all elements in the periodic table.

For the first time, a team has detected rhodium in the +7 oxidation state, the third highest oxidation state experimentally among all elements in the periodic table. © https://doi.org/10.1002/anie.202207688

Oxidation states of transition metals describe how many electrons of an element are already engaged in bonding, and how many are still available for further reactions. Scientists from Berlin and Freiburg have now discovered the highest oxidation state of rhodium, indicating that rhodium can involve more of its valence electrons in chemical bonding than previously thought. This finding might be relevant for the understanding of catalytic reactions involving highly-oxidized rhodium. The result was recognized as a „very important paper“ in Angewandte Chemie.

Transition metals in high or unusual oxidation states might play an important role as catalysts or reaction intermediates in chemical reactions. Because transition metals are already well characterized in most cases, the discovery of a new oxidation state of rhodium came as a real surprise. The identification of rhodium(VII) was made possible by PhD student Mayara da Silva Santos and co-workers, who were able to isolate the species from any reactant in a low-temperature ion trap, and perform x-ray absorption spectroscopy for its characterization. 

BESSY II was essential for the discovery

These kinds of experiments are highly demanding, and can, at present, only be carried out at BESSY II. „The combination of advanced sample preparation, low-temperature ion trapping, and x-ray spectroscopy is unique. Because these essential tools can even be applied to more complex systems, we anticipate further insight into exotic transition metal oxides“, says Vicente Zamudio-Bayer, head of the ion trap group at beamline UE52-PGM, who develops and operates the ion trap endstation at BESSY II. „What was important for us was that our surprising experimental findings could be substantiated by Sebastian Riedel‘s group at FU Berlin, who performed state-of-the-art calculations on the species in question“, explains Zamudio-Bayer. “Even rhodium in oxidation state +6 is very rare, so we had to be extremely careful about +7. New oxidation states are not discovered every day”, says Mayara da Silva Santos.

Catalytic relevance of a potential reaction intermediate

“This is the third-highest oxidation state of all elements. The fact that rhodium(VII) exists, but was unknown, could imply that it might have been overlooked when analyzing pathways of chemical reactions”, Zamudio-Bayer points out.

Possible stabilization for further use

The discovery of rhodium(VII) was made for gas-phase species, but a stabilization of the trioxidorhodium cation by weakly coordinating anions seems possible, based on comparison with other known compounds . This could open prospects for further characterization or applications. “Our rhodium(VII) species is highly reactive, but understanding these seemingly exotic species could lead to improved materials in the future,” Mayara da Silva Santos adds.

Tobias Lau


You might also be interested in

  • A simpler way to inorganic perovskite solar cells
    Science Highlight
    17.04.2024
    A simpler way to inorganic perovskite solar cells
    Inorganic perovskite solar cells made of CsPbI3 are stable over the long term and achieve good efficiencies. A team led by Prof. Antonio Abate has now analysed surfaces and interfaces of CsPbI3 films, produced under different conditions, at BESSY II. The results show that annealing in ambient air does not have an adverse effect on the optoelectronic properties of the semiconductor film, but actually results in fewer defects. This could further simplify the mass production of inorganic perovskite solar cells.
  • Spintronics: A new path to room temperature swirling spin textures
    Science Highlight
    16.04.2024
    Spintronics: A new path to room temperature swirling spin textures
    A team at HZB has investigated a new, simple method at BESSY II that can be used to create stable radial magnetic vortices in magnetic thin films.

  • BESSY II: How pulsed charging enhances the service time of batteries
    Science Highlight
    08.04.2024
    BESSY II: How pulsed charging enhances the service time of batteries
    An improved charging protocol might help lithium-ion batteries to last much longer. Charging with a high-frequency pulsed current reduces ageing effects, an international team demonstrated. The study was led by Philipp Adelhelm (HZB and Humboldt University) in collaboration with teams from the Technical University of Berlin and Aalborg University in Denmark. Experiments at the X-ray source BESSY II were particularly revealing.