Ruthenium-Hydride Assisted Remarkable Diversity Towards Non-Spectator Feature of Benzodifuroxan

The present article demonstrates that ruthenium-hydride [Ru^II (H)(Cl)(CO)(PPh₃ )₃ ] mediated diverse functionalization modes of benzodifuroxan (BDF) encompassing two furoxan rings. Hydride transfer from the metal precursor facilitated multiple cascade reactions involving unsymmetrical cleavage of the furoxan rings of BDF, leading to the one-pot formation of a series of ruthenium (II) coordinated functionalized ligands exhibiting bidentate κ² -N,O, κ² -N,N' and bis-bidentate μ-bis(κ² -N,O) modes. Further, a moderately stable intermediate species was also encountered in the reaction sequence in which the transformed deoxygenated ligand coordinated to the metal ion via the rarely manifested furazan ring (κ² -N,N'' mode). The products were authenticated by their single-crystal X-ray structures and other spectroscopic/analytical techniques. Redox non-innocence of the functionalized ligands in the complexes was illustrated by spectroelectrochemistry (cyclic voltammmetry, UV-Vis. and EPR) in conjunction with DFT/TD-DFT calculations. Mechanistic outline for the facile ring opening processes of BDF including interconversions of complexes (e. g. reductive ring opening) were also addressed.