Advancing White Phosphorus Functionalisation Through Main Group Catalysis

• Applicant: Professor Dr. Robert Wolf
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 548830090

The aim of this project is the development of main group element catalysts for the synthesis of monophosphorus compounds from white phosphorus (P4). Catalytic transformations of P4 were little known until recently, but are increasingly gaining importance. Despite numerous literature studies on the stoichiometric activation of P4, the potential of main group element compounds as catalysts for P4 functionalisation is still poorly understood. Building on successful preliminary work on hydrostannylation, hydrogermylation and hydrosilylation of P4, the first part of this project will investigate the application of such group 14 element compounds in more detail. The synthesis potential of group 14 hydrides and distannanes will be tested and closed synthetic cycles will be developed by recovery and reutilisation of group 14 reagents. The knowledge gained should lead to a detailed mechanistic understanding that will be utilised for the development of new catalytic transformations using readily available reducing agents or electrochemical reduction processes. In the second part of the project, catalysis concepts based on the oxidation of P4 with chalcogen compounds (disulphides and quinones) and with halogens will be developed. The functionalisation of P4 using these reagents will be investigated in detail and suitable conditions for recycling and regeneration of the reagents will be determined. The knowledge gained will form the basis for new catalytic processes. The planned investigations aim at the academic foundations for main group-catalysed transformations of P4. This will lay essential groundwork for the future development of efficient P4 functionalisation methods, which can replace traditional chlorine-based routes in the long term.

• DFG Programme: Research Grants
• International Connection: United Kingdom
• Cooperation Partner: Dr. Daniel J. Scott