Diaryliodonium as a double σ-hole donor: the dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations

Abstract

The reactivity of [Ar¹Ar²I](SCN) toward the solid-state arylation depends on the preorganization of halogen bond (XB)-bound SCN⁻: <italic>N</italic>-XB-bound thiocyanates, which, in contrast to <italic>N</italic>,<italic>S</italic>-XB-bound, undergoes the extremely rare <italic>N</italic>-arylation of SCN⁻.