Stimuli Responsive Silylene: Electromerism Induced Reversible Switching Between Mono‐ and Bis‐Silylene

Electromerism is a very well-known phenomenon in transition metal chemistry. In main group chemistry, this concept has only started getting attention recently. We report stimuli responsive low-valent silicon compounds exhibiting electromerism. A mixed-valent silaiminyl-silylene 1, [LSi−Si(NDipp)L] (L=PhC(N$^t$Bu)$_2$), was synthesized in a single step from amidinate-chlorosilylene. Compound 1 has two interconnected Si atoms in formally +I and +III oxidation states. Upon treatment with Lewis acidic Cu$^I$X (X=mesityl, Cl, Br, I), electron redistribution occurs resulting in the formation of [{LSi(NDipp)Si(L)}−CuX], in which both silicon atoms are in the +II formal oxidation state. Removal of the copper center from [{LSi(NDipp)Si(L)}−CuX] by using a Lewis basic carbene led to reformation of the precursor [LSi−Si(NDipp)L]. Thus, the process is fully reversible. This showcases the first example of Lewis acid/base-induced reversible electromerism in silicon chemistry.