Chem. Sci., 2026, Accepted Manuscript DOI: 10.1039/D6SC04320H, Edge Article Torben Rogge, Wolfgang Obermayer, Martin Oestreich A quantum-chemical investigation of the palladium-catalyzed cross-coupling of silylated diazenes as diazenyl anion equivalents and aryl electrophiles is reported. The selectivity, that is azobenzene formation by diazenylation versus biaryl formation...