Valence Tautomerism of p‐Block Element Compounds – An Eligible Phenomenon for Main Group Catalysis?

Valence tautomerism has had a remarkable impact on several branches of transition metal chemistry. By switching between different valence tautomeric states, physicochemical properties and reactivities can be triggered reversibly. Is this phenomenon transferrable into the p‐block – or is it already happening there? This Perspective collects observations of p‐block element‐ligand systems that might be assignable to valence tautomerism. Further, it discusses occurrences in p‐block element compounds that exhibit the related effect of redox‐induced electron transfer. As disclosed, the concept of valence tautomerism with p‐block elements is at a very early stage. However, given the substantial disparity in the properties of those elements in different redox states, it might offer a valid extension for future developments in main group catalysis.