Ru-Complex Framework toward Aerobic Oxidative Transformations of β‑Diketiminate and α‑Ketodiimine

The impact of the {Ru­(acac)₂} (acac^– = acetylacetonate) framework on the transformations of C–H and C–H/C–C bonds of coordinated β-diketiminate and ketodiimine scaffolds, respectively, has been addressed. It includes the following transformations involving {Ru­(acac)₂} coordinated β-diketiminate in 1 and ketodiimine in 2 with the simultaneous change in metal oxidation state: (i) insertion of oxygen into the C­(sp²)–H bond of β-diketiminate in 1, leading to the metalated ketodiimine in 2 and (ii) Bronsted acid (CH₃COOH) assisted cleavage of unstrained C­(sp²)–C­(sp²)/CN bonds of chelated ketodiimine (2) with the concomitant formation of intramolecular C–N bond in 3, as well as insertion of oxygen into the C­(sp³)–H bond of 2 to yield −CHO function in 4 (−CH₃ → −CHO). The aforesaid transformation processes have been authenticated via structural elucidation of representative complexes and spectroscopic and electrochemical investigations.