Rational Design and Smart Synthesis of Non-Transition-Metal Systems for Small Molecules Activation (SM-Act)

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Small molecules activation by non-transition metal systems (i.e. main-group compounds) is challenging. Thermally stable main-group compounds with a reactivity and properties comparable to open-shell transition-metal complexes are therefore appealing synthetic targets. This proposal aims at the exploration of phosphorus- and arsenic-centered radical and radicaloid compounds stabilized by unconventional carbon-donor ligands, namely N-heterocyclic vinyl (NHV) and N-heterocyclic vinylidene (NHVD) ligands. These ligands are very strong delta- as well as pi-donors. Moreover, their electronic and steric features provide a unique platform for the delocalization of unpaired electron spin density, leading to the formation of very stable molecular frameworks containing a C2E2, C2EE′, C2E4, or C2E2E′2 moiety (usually rings) (E = P, E′ = As). Systematic experimental and theoretical studies of the proposed compounds will enable us to understand their electronic structure and bonding situation, as well as their reactivity with small molecules (e. g. H2, O2, CO, N2O, CO2 etc). The impact of the ligand architecture on the structure and properties of proposed compounds will be studied to outline the key factors that regulate their properties. Investigation of such open-shell main-group species is not only important to enhance our understanding about chemical bonding but also to recognize their potential applications in synthesis and materials science.