Thermal and Photochemical Reactions of Azidoruthenium(III) Complexes of Macrocyclic Tertiary Amines and the Structure of the (Phosphoraniminato)ruthenium(III) Complex trans ‐[Ru(14‐TMC)(N 3 )(NPPh 3 )] +

The bis(azido)ruthenium(III) complexes, trans ‐[Ru(L)(N 3 ) 2 ] + [L = 14‐TMC ( 1 ) and 16‐TMC ( 4 )] have been prepared. These complexes undergo facile thermal or photo‐decomposition in RCN (R = Me, Bu, Ph, 4‐MePh, 2‐MeOPh) solutions to produce the corresponding azidoruthenium(II) complexes trans ‐[Ru(L)(N 3 )(RCN)] + [L = 14‐TMC, R = Me ( 2a ), Bu ( 2b ), Ph ( 2c ), 4‐MePh ( 2d ), 2‐MeOPh ( 2e ); L = 16‐TMC, R = Me ( 5a ), = Ph ( 5b )] and cis ‐[Ru(Tet‐Me 6 )(N 3 )(MeCN)] + ( 6 ). Complex 1 reacted with PPh 3 , by a nitrogen atom transfer reaction, to give trans ‐[Ru(14‐TMC)(N 3 )(NPPh 3 )] + ( 3 ) in 80 % yield. The crystal structures of 2e (PF 6 ), 3 (PF 6 ) and 5b (ClO 4 ) have been determined by X‐ray diffraction analysis. Complex 3 is the first structurally characterized (phosphoraniminato)ruthenium(III) complex with Ru–N distances of 1.991(7)–2.014(6) Å and a nearly linear Ru–N–P moiety [[ang]Ru–N–P = 168.2(5)–171.5(6)°]. Density functional theory (DFT) calculations on 3 and the proposed [Ru V (14‐TMC)(N)(N 3 )] + intermediate have been performed.