A Mononuclear Ruthenium(V)‐Imido Complex With Hydrogen Bonding in the Second Coordination Sphere Forming Aziridines Without <i>N</i> ‐Substituents From Alkenes in Water

ABSTRACT Aziridines are class of organic molecules that have a nitrogen‐containing three‐membered ring structure. These heterocyclic compounds have garnered recent interest owing to their bioactivity and intermediacy in the synthesis of value‐added products, such as pharmaceuticals. However, it is difficult to efficiently prepare aziridines that do not have N ‐substituents. This study employs a ruthenium(V)‐imido (Ru V ═NH) complex ( 2 ) with hydrogen‐bonding (HB) sites in the second coordination sphere (SCS) to selectively synthesize such aziridines. Notably, 2 oxidizes alkenes in water via nitrogen‐atom transfer to the alkene substrate, thereby producing aziridine derivatives without N ‐substituents in high yields. In contrast, an Ru V ═NH complex without HB sites in the SCS generates allylic alcohols via hydrogen‐atom transfer in water. The aziridination of alkenes by 2 is influenced by the electron density and steric hindrance of the C═C double bond in the substrate.