Multiple Metal–Metal Bond or No Bond? The Electronic Structure of V 2 O 2

Detailed knowledge of the electronic structure of vanadium oxide clusters provides the basis for understanding and tuning their significant catalytic properties. However, already for the simple four‐atom V 2 O 2 molecule, there are contradictory reports in the literature regarding the electronic ground state and a possible vanadium–vanadium bond. We herein show through a combination of experimental (matrix isolation) studies and theoretical results that there is a multiple vanadium–vanadium bond in this benchmark vanadium oxide molecule.