This work presents three mononuclear Ru(II) complexes of tridentate phosphine-carboxamide based ligands providing NNP coordination environment. The octahedral Ru(II) ion receives additional coordinations from co-ligands; CO, Cl and CH3OH. All...

We present synthesis and characterization of two half-sandwich Ru­(II) complexes supported with amide-phosphine based ligands. These complexes presented a pyridine-2,6-dicarboxamide based pincer cavity, decorated with hydrogen bonds, that participated in the binding of nitro-substrates closer to the Ru­(II) centers, which is further supported with binding and docking studies. These ruthenium complexes functioned as the noteworthy catalysts for the borohydride mediated reduction of assorted nitro-substrates. Mechanistic studies not only confirmed the intermediacy of [Ru–H] in the reduction but also asserted the involvement of several organic intermediates during the course of the catalysis. A similar Ru­(II) complex that lacked pyridine-2,6-dicarboxamide based pincer cavity substantiated its unique role both in the substrate binding and the subsequent catalysis.

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Cobalt complexes of amide‐based ligands appended with protonated heterocyclic rings are utilized as the earth‐abundant catalysts for the transfer hydrogenation of assorted carbonyl compounds using isopropanol as the hydrogen source. The most successful complex illustrated remarkable catalytic performance towards a wide range of aldehydes and ketones, quantitatively yielding primary and secondary alcohols as the products, respectively. The catalysis scope also included a few biologically relevant substrates such as furfural, vanillin, ortho‐vanillin, coumarin and chalcone. The substrate binding, Hammett, kinetic and DFT studies provided the mechanistic insights.