Synthesis and catalytic activity of μ-​oxo ruthenium(IV) porphyrin species to promote amination reactions

This work describes the synthesis of ruthenium(IV) mu-oxo porphyrin complexes of general formula [Ru-IV(TPP)(X)](2)O which have been applied as catalysts in nitrene transfer reactions using aryl azides (ArN3) as nitrene sources. Collected data indicated that the catalytic efficiency of [Ru-IV(TPP)(OCH3)](2)O was comparable to that of Ru-II(TPP)CO because of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species Ru-VI(TPP)(ArN)(2). The reaction of [RuIV(TPP)(OCH3)](2)O with Ph3CN3 or (CH3)(3)SiN3 afforded [RuIV(TPP)(N-3)](2)O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.