Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform

An unprecedented reactivity profile of biochemically relevant R‐benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac) 2 } (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [Ru III (acac) 2 (L 1R )] ( 1 a – 1 c ; L 1R =2‐nitrosoanilido derivatives) and dimeric [{Ru II (acac) 2 } 2 (L 2R )] ( 2 a – 2 b ; L 2R =(1 E ,2 E )‐ N 1 , N 2 ‐bis(2‐nitrosophenyl)ethane‐1,2‐diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH − in the former and solvent‐assisted multiple N−C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C 2 D 5 OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L 1 and L 2 in 1 and 2 , respectively, was also probed by spectroelectrochemistry in combination with DFT calculations.