Synthesis and Reactivity of Phosphatetrahedranes and Related Species: New Phosphaorganic Building Blocks

• Applicant: Professor Dr. Robert Wolf
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 451444676

Tetrahedranes are highly strained and reactive organic molecules comprised of four carbon at-oms in a tetrahedral arrangement. They have been of considerable interest due to their scarcity and increased reactivity resulting from high bond strain. Due to the difficulty of isolating such species the tetrahedrane family is limited, and neutral heteroatomic tetrahedranes were almost unknown until very recently. The synthesis of di-tert-butyldiphosphatetrahedrane, (tBuCP)2, re-ported by our group in late 2019, and the report of tri-tert-butylphosphatetrahedrane, (tBuC)3P by C. C. Cummins and co-workers in March 2020 have opened exciting opportunities in this previ-ously dormant research field. This project will systematically study the chemistry of the phosphatetrahedranes to understand their synthesis, chemical properties and reactivity. This will open a path toward their utilization as versatile building blocks for phosphaorganic and phosphaorgan-ometallic compounds. The investigations will focus on the isolation of a wider variety of phosphatetrahedranes, followed by the study of their interaction toward fundamental reagents such as electrophiles, nucleophiles and reducing agents, and their coordination chemistry with transition metals. The project particularly focusses on the chemistry of diphosphatetrahedranes, but the synthesis of related mono- and triphosphatetrahedranes is likewise investigated. In particular, we intend to compare the behavior of the new family of phosphatetrahedranes with that of the most relevant inorganic tetrahedrane known to date, white phosphorus (P4). It is anticipated that the fundamental investigations proposed in this project will deliver a profound understanding of the chemistry of phosphatetrahedranes. In addition, this will lay the ground for the discovery of further unusual organophosphorus compounds.

• DFG Programme: Research Grants