A Curious Case Of Pnictogen Cations
Roman Dobrovetsky
School of Chemistry, Tel Aviv University, Tel Aviv, Israel
Group 15 species have attracted considerable attention for their potential to activate small molecules and mediate catalytic transformations. In particular, structurally constrained pnictogen centers have emerged as promising platforms for transition-metal-like reactivity.
Our research focuses on structurally constrained Pn(III) and Pn(V) cations (Pn = pnictogen), which exhibit distinct but complementary reactivity patterns. As we have recently demonstrated for P(III) systems, structural constraint can promote ambiphilic small-molecule activation and transition-metal-mimicking catalysis. In contrast, P(V) cations can exhibit exceptional Lewis acidity, enabling small-molecule activation and catalytic transformations. In this talk, I will highlight the potential of structurally constrained pnictogen cations as versatile platforms for small-molecule activation and catalysis, presenting recent advances in the chemistry of these species. These include H2 activation and metallomimetic catalytic hydrogenation mediated by constrained P(III) cations, C–Si bond activation by a structurally constrained Sb(III) cation followed by catalytic silane redistribution, and the development of novel P(V)-based Lewis superacids and their reactivity toward small molecules.