Exploring the Limits of High Potential Oxidizers Prediction, Validation and Preparation of Unusual Molecules at the Edge of Stability

Project Information

HighPotOx

Grant agreement ID: 818862

DOI

10.3030/818862

Project closed

EC signature date 18 February 2019

Start date 1 January 2020

End date 31 December 2025

Funded under

• EXCELLENT SCIENCE - European Research Council (ERC)

Total cost

€ 1 988 280,00

EU contribution

€ 1 988 280,00

Coordinated by

FREIE UNIVERSITAET BERLIN
Germany

Periodic Reporting for period 3 - HighPotOx (Exploring the Limits of High Potential OxidizersPrediction, Validation and Preparation of Unusual Molecules at the Edge of Stability)

Reporting period: 2023-01-01 to 2024-06-30

Summary of the context and overall objectives of the project

Unusual species show unusual reactivity! The HighPotOx project aims at the prediction, validation as well as molecular isolation and bulk preparation of high to extreme potential oxidizers, which in most cases correlate with their existence in high oxidation states. That is why both aspects cannot be studied independently. However, additional factors unrelated to a physical oxidation state influence the oxidizing strength. As known, the electron affinity, which can be used as a scale for the oxidizing strength, increases from its anionic via neutral to the cationic nature of the compounds, while their oxidation state remains constant. Furthermore, the acidity of the solvent also plays a key role in synthetic strategies. Basic solvents prefer the formation of anions, while an acidic environment leads to the stabilization of cations. Keeping this concept in mind, it will be more advantageous to investigate and stabilize bulk quantities of compounds in extreme oxidation states in their neutral or anionic form. The formation of cations is undoubtedly more challenging.
Due to their potential interest and due to their industrial applications, the HighPotOx project aims as well at the investigation of oxygen-containing potential oxidizers and their oxidation states. Its bonding characteristic to the central atom can be characterized, e.g. based on vibrational spectroscopy and quantum-chemical methods.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

The ERC project HighPotOx investigated a plethora of new fundamental oxidizers via matrix-isolation spectroscopy in conjunction with quantum-chemical methods such as CN+, MF6, HgO3 to mentioned only a few. One of the fundamental achievements in this series is the discovery and characterization of a new oxidation state of rhodium in Rh(VII)O3+. This new species is also expected to be a potential strong oxidizer. Further scientific achievements have been made by bulk preparation. The application of the polychloride ionic liquid as oxidizing reagent to prepare the so far unknown and surprising [SCl6]2- dianion is one of the highligths. A further achievement is the synthesis and characterization of the perfluorinated trityliumion. Which can now be prepared in larger quantities and can be handled at room temperature. This novel oxidizer will be a useful reagent in further chemistry applications. represents a breakthrough into a possible synthetic chemistry of the so far unknown transition metal ozonides and perhaps a new class of compounds with surprising properties.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

In the HighPotOx project we propose to combine different techniques to systematically investigate high potential fluorinated and non-fluorinated oxidizers as well as molecular species bearing elements in high oxidation states. The results, which we gain by a combination of sophisticated experimental and theoretical methods will guide us in the discovery of new trends and concepts towards an understanding of prototype problems encountered with high potential oxidants at the frontiers of chemistry.

Structure of the HighPotOx project