Isolation of Silylene-Ligated Plumbyliumylidene andDiplumbyne

In this study, we present the synthesis and characterization of bis­(silylene)-ligated plumbyliumylidene and silylene-ligated diplumbyne. Plumbyliumylidene <b>2</b> was obtained through ion–exchange reaction of the bis­(silylene)­amido lead­(II) bromide complex <b>1</b> with one equivalent of Na­[BAr^F₄] (Ar^F = 3,5-(CF₃)₂-C₆H₃). Density functional theory calculations confirmed the presence of a lone pair on the lead atom in <b>2</b>. The reduction of compound <b>2</b> yielded silylene-ligated diplumbyne <b>3</b>, which possesses a Pb–Pb single bond and one lone pair on each lead atom. Remarkably, compound <b>3</b> underwent single-electron oxidation to regenerate plumbyliumylidene <b>2</b>, demonstrating a rare redox cycle between the Pb­(I) and Pb­(II) states. This study enhances the understanding of the electronic structures and redox behavior of low-valent lead compounds.