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

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journal contribution
posted on 2017-11-30, 20:19 authored by Sanjib Panda, Abhishek Mandal, Prabir Ghosh, Goutam Kumar Lahiri
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.