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Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform
Author(s) -
Ghosh Prabir,
Dey Sanchaita,
Panda Sanjib,
Lahiri Goutam Kumar
Publication year - 2018
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.201800308
Subject(s) - diimine , chemistry , surface modification , solvent , reactivity (psychology) , ruthenium , monomer , electrochemistry , pyrrole , ligand (biochemistry) , medicinal chemistry , combinatorial chemistry , photochemistry , organic chemistry , catalysis , polymer , electrode , medicine , biochemistry , alternative medicine , receptor , pathology
An unprecedented reactivity profile of biochemically relevant R‐benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac) 2 } (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [Ru III (acac) 2 (L 1R )] ( 1 a – 1 c ; L 1R =2‐nitrosoanilido derivatives) and dimeric [{Ru II (acac) 2 } 2 (L 2R )] ( 2 a – 2 b ; L 2R =(1 E ,2 E )‐ N 1 , N 2 ‐bis(2‐nitrosophenyl)ethane‐1,2‐diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH − in the former and solvent‐assisted multiple N−C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C 2 D 5 OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L 1 and L 2 in 1 and 2 , respectively, was also probed by spectroelectrochemistry in combination with DFT calculations.