Trichlorosilyl Anions of p‐Block Elements – New Applications for Simple Molecules

Recently several trichlorosilyl anions of main group elements have been isolated and characterized. Since 2015 anions [E(SiCl3)n]−, which are stabilized solely by trichlorosilyl groups, have been prepared with E=B, C, Si, Ge, P, S. These compounds have long been overlooked due to their high reactivity. This disadvantage is also an advantage, since the high reactivity makes these anions useful as reagents in a number of transformations. Anions of this kind have been used so far in substitution reactions, as superacids, and weakly coordinating anions. This review summarizes present methods for the synthesis of these compounds. Possible applications and future developments are outlined. Structurally characterized trichlorosilyl anions of p‐block elements have recently been shifted into the focus of research due to their outstanding properties. The anions [E(SiCl3)n]− (E=B, C, Si, Ge, P, S) are stabilized solely by trichlorosilyl groups. Anions of this kind are potential nucleophilic transfer reagents for SiCl3‐groups and p‐block elements. They could serve as superacids and weakly coordinating anions.