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Ruthenium‐Hydride Assisted Remarkable Diversity Towards Non‐Spectator Feature of Benzodifuroxan
Author(s) -
Dey Sanchaita,
Panda Sanjib,
Lahiri Goutam Kumar
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000849
Subject(s) - ruthenium , chemistry , hydride , denticity , furoxan , ring (chemistry) , ligand (biochemistry) , metal , photochemistry , crystallography , stereochemistry , crystal structure , medicinal chemistry , organic chemistry , catalysis , biochemistry , receptor , nitric oxide
The present article demonstrates that ruthenium‐hydride [Ru II (H)(Cl)(CO)(PPh 3 ) 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 κ 2 ‐N,O, κ 2 ‐N,N′ and bis‐bidentate μ‐bis(κ 2 ‐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 (κ 2 ‐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.