| Abstract: | The synthesis and structural characterization of two azirine rhodium(III ) complexes are described. The stabilization, N‐coordination and phenylgroup π‐stacking of the highly reactive and strained 3‐phenyl‐2H‐azirine by transition metal coordination is observed. The reaction of the dimeric complex [(η5‐C5Me5)RhCl2]2 with 3‐phenyl‐2H‐azirine (az) in CH2Cl2 at room temperature in a 1:2 molar ratio afforded the neutral mono‐azirine complex [(η5‐C5Me5)RhCl2(az)]. The subsequent reaction of [(η5‐C5Me5)RhCl2]2 with six equivalents of az and 4 equivalents of AgOTf yielded the cationic tris‐azirine complex [(η5‐C5Me5)Rh(az)3](OTf)2. After purification, all complexes have been fully characterized. The molecular structures of the novel rhodium(III ) complexes exhibit slightly distorted octahedral coordination geometries around the metal atoms. |
