A simple, straightforward and atom economic strategy to the synthesis of 1,3‐disubstituted imidazo[1,5‐a]pyridines using binuclear ruthenium(II) catalyst through acceptorless dehydrogenative coupling of primary alcohols with 2‐benzoylpyridine has been presented. New binuclear arene Ru(II) N^O chelating complexes of common formula [(η6‐benzene)2Ru2Cl2(μ‐L)], L = bis (furoylhydrazone) derivatives (1–3) were synthesized and characterized by analytical and spectral (FT‐IR, NMR and HR‐MS) techniques. The solid‐state molecular structure of one of the complexes (complex 1) has been authorized by single‐crystal XRD method. Further, a wide range of 1,3‐disubstituted imidazo[1,5‐a]pyridine derivatives have been successfully attained in good to excellent yields using binuclear arene Ru(II) catalysts with 1.0 mol% of catalyst loading. Further, control experiments unveil that the dehydrogenative coupling reaction mechanism proceeds via the formation of aldehyde and imine intermediates. The overall catalytic system releases H2 and water as only valuable by‐products.

Dinuclear Ru(ii) furoylhydrazone complexes are synthesized and characterized. Further, the cytotoxicity of the complexes is explored. The apoptotic cell death pathway is confirmed with aid of AO-EB, DAPI staining and quantified by flow cytometry.