Development of N-Heterocyclic Carbene Phosphinidene-substituted Tetrylenes for Small Molecule Activation and Catalysis

• Applicant: Professor Dr. Shigeyoshi Inoue
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 573309611

The last half century has seen monumental development in the realm of main group chemistry, a key area being the isolation of low oxidation state p-block complexes. Such compounds have demonstrated multifaceted capabilities, including bond activation and catalysis. One group that has seen tremendous growth is Group 14, especially its heavier elements. It has been found that the chemistry of the tetrels in the +2 oxidation state is very rich, particularly in their monomeric “tetrylene” form, L2E (E = Si-Pb, L = ligand), due to their ambiphilic nature. We have developed many tetrylene systems and have recently found the use of N-heterocyclic imines (NHI) as ligands to be very effective. Utilising NHIs, we have synthesised a plethora of fundamentally important compounds which have demonstrated new reactivities unprecedented in main-group chemistry. The main objectives of this project is to further this chemistry by utilising N-heterocyclic carbene phosphinidenes (NHCP) as a new ligand class for tetrylene chemistry. The work programme contains two parts. WP-1 will focus on the synthesis of NHCP stabilised tetrylenes of the general formula, L(NHCP)E (E = Si-Pb, L = ligand). WP-2 concerns the reactivity studies of the complexes isolated from WP-1. This will include bond activation processes, involving δ- and π-bonded systems and further functionalisation of substrates. These initial reactivity studies will then lead to an examination of the catalytic capabilities of these L(NHCP)E complexes. The electronic nature of these compounds, as well as their reactivity, will be studied using state-of-the-art computational methods.

• DFG Programme: Research Grants