Organoxenon Compounds as Versatile Oxidizers in Organometallic Chemistry (OrgXeMet)

• Applicant: Dr. Alberto Pérez-Bitrián
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 555630982

A plethora of organoxenon species, i.e., containing Xe−C bonds are known and despite their reactivity as electrophilic-transfer reagents has been demonstrated, their suitability as oxidizers in transition metal chemistry has not been explored yet. The aim of OrgXeMet is the investigation of the potential of organoxenon compounds as versatile oxidizers towards organometallic complexes, able to simultaneously transfer an organic group with high atom economy. To achieve this goal, a systematic investigation of the synthesis, behavior and properties of different families of organoxenon(II) compounds is planned initially, which will eventually lead to the generation of a toolbox of reagents that can be used for target-specific processes. Diverse organoxenonium(II) [RXe]+ ions containing different types of organic groups (R = aryl, alkenyl, alkynyl) featuring varying degrees of fluorination will be prepared, with a special focus on groups that can improve the properties of the compounds in terms of stability and/or reactivity. The synthesis of neutral organoxenon(II) fluorides, RXeF, and diorganoxenon(II) species, RXeR’, will be also tackled. With all the gathered knowledge, these species will be employed for preparing unprecedented 3d-metal complexes with relevance to current topics in organometallic chemistry. In particular, they will be used for the synthesis of Ni and Cu complexes in formal high oxidation states, whereby the organic group(s) will be electrophilically transferred to the metal center and only gaseous Xe will be released. Focusing on nickel, Ni(III) and Ni(IV) complexes are of interest, since they hold a pivotal role in Ni-mediated and -catalyzed processes, yet isolable species that allow for comprehensive characterization remain scarce. Our strategy to cleanly incorporate an organofluorine ligand into the metal center with an organoxenon reagent will allow to synthesize a large variety of these complexes. Mechanistic studies for such key transformation with the vision for the development of cross-coupling processes will be performed. On the other hand, the organoxenon species should be powerful enough to access Cu(III) complexes with fluorinated ligands different than CF3, yielding new types of organocopper(III) complexes and enabling the pioneering investigation of the phenomenon of ligand field inversion with a variety of different ligands. This will imply not only the use of state-of-the-art quantum chemical calculations to disentangle the electronic structure of the complexes, but also modern spectroscopic methods to determine the “physical” oxidation state of the prepared compounds. All in all, OrgXeMet entails a project merging the fields of main-group chemistry and transition metal chemistry within the frame of fluorine chemistry, offering an original synthetic strategy with many potential applications.

• DFG Programme: Emmy Noether Independent Junior Research Groups
• Major Instrumentation: Glovebox
• Instrumentation Group: 4670 Handschuhkästen, Schutzgasanlagen