A Half‐Sandwich Ruthenium Complex With 1‐Nitroso‐2‐naphthol: Utilization of Ligand Dissociability Toward Synthesis and Catalysis

ABSTRACT Reaction of 1‐nitroso‐2‐naphthol (Hnn) with [{Ru( p ‐cymene)Cl 2 } 2 ] afforded [Ru( p‐ cymene)(nn)Cl], ( 1 ), in good yield. Attempted chloride abstraction from 1 via its interaction with Ag + in acetonitrile medium led to chloride removal, associated with displacement of the p ‐cymene by acetonitrile, yielding [Ru(nn)(CH 3 CN) 4 ]PF 6 , ( 2 ). The favorable thermodynamics behind conversion of 1 to 2 was found out by DFT calculation. The potential of 2 as a precursor for synthesis of new complexes retaining the Ru(nn) moiety was examined by its reaction with 2,2ʹ‐bipyridine (bpy), which afforded [Ru(nn)(bpy) 2 ]PF 6 , ( 3 ). Preliminary characterization of 1 – 3 was done by different spectral techniques. Crystal structures of all the complexes were determined, which revealed their stereochemistry and binding modes of the different ligands in them. Electronic absorption spectra of the complexes displayed intense absorptions in the visible and ultraviolet regions, the origin of which was probed with TDDFT method. Electrochemical redox properties of 1 – 3 were also investigated by cyclic voltammetry. Potential of 1 as a catalyst‐precursor was explored toward two types of reactions, transfer‐hydrogenation of aldehydes to alcohols and hydration of nitriles to amides, and it showed notable efficiency in catalyzing both the reactions. Probable mechanisms for the observed catalytic reactions were proposed.