Role of ligand disposition and oxime…oximato hydrogen bonding upon redox non-innocent character of rhodium(III) phenylazooximates. (1st May 2023) - Naskar, Srijita
Graphical abstract: Redox noninnocent behavior of rhodium phenylazooxime complex has been accomplished by suitable disposition of ligands and interplay of oxime….oximato intramolecular hydrogen bonding. Abstract: The diaryl-azo-oxime ligands HL, 1 undergoes oxidative coordination reaction with Wilkinson's catalyst to form two isomeric complexes of type cis -[Rh III L2 Cl(PPh3 )], 2a (Cl and PPh3 are cis ) and trans -[Rh III L2 Cl(PPh3 )], 2b where they are trans with respect to each other. Unlike the case of 2a, the complex 2b upon treatment with sodium borohydride, can be transformed to trans -[Rh III (HL ● )(L – )Cl(PPh3 )], 3 and the reaction appears to progress via PCET. The disposition of ligand frameworks as well as the formation of oxime…oximato hydrogen bond appears to have a significant function for phenylazooxime to exhibit redox non-innocent behaviour in presence of rhodium(III). The compounds were characterized by electrochemical analysis, different spectral methods, single crystal XRD and optoelectronic properties, particularly the nature of transitions in the chelates were scrutinized by TD-DFT.