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

The impact of the {Ru(acac)} (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)} coordinated β-diketiminate in 1 and ketodiimine in 2 with the simultaneous change in metal oxidation state: (i) insertion of oxygen into the C(sp)-H bond of β-diketiminate in 1, leading to the metalated ketodiimine in 2 and (ii) Bronsted acid (CHCOOH) assisted cleavage of unstrained C(sp)-C(sp)/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(sp)-H bond of 2 to yield -CHO function in 4 (-CH → -CHO). The aforesaid transformation processes have been authenticated via structural elucidation of representative complexes and spectroscopic and electrochemical investigations.