• Balaji R Jagirdar

      Articles written in Journal of Chemical Sciences

    • Dependence of the cone angles of phosphorus-containing ligands in the chemistry of hydride and dihydrogen complexes of ruthenium

      Nisha Mathew Balaji R Jagirdar

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    • Snapshots of the “breaking” of the H-H bond in the oxidative addition of H2 to a metal centre

      Saikat Dutta Balaji R Jagirdar

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      Three new monocationic molecular hydrogen complexes of ruthenium of the typetrans-[RuCl(η2-H2)(PP)2][BF4] (PP = bis-l,2(diarylphosphino)ethane, aryl = p-fluorobenzyl, benzyl,p-methyl-benzyl) have been prepared by protonating the precursor hydride complexes trans-[RuCl(H)(PP)2] using HBF4.Et20. These three dihydrogen complexes are quite stable and have been isolated in the solid state. The intact nature of the H-H bond in these derivatives has been established from the short spin-lattice relaxation times(T1, ms) and the observation of substantial H, D couplings in the HD isotopomers. The H-H bond distances(dHH, å) increase from 0.97 to 1.01 å as the electron donor ability of the diphosphine ligand increases from the p-fluorobenzyl to the benzyl to the p-methylbenzyl moiety. These dihydrogen complexes constitute the initial stages of elongation of the H-H bond enroute to its cleavage along the reaction coordinate for the oxidative addition of H2 to a metal centre.

    • Digestive ripening: a synthetic method par excellence for core-shell, alloy, and composite nanostructured materials

      Srilakshmi P Bhaskar Balaji R Jagirdar

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      The solvated metal atom dispersion (SMAD) method has been used for the synthesis of colloids of metal nanoparticles. It is a top-down approach involving condensation of metal atoms in low temperature solvent matrices in a SMADreactor maintained at 77 K.Warming of the matrix results in a slurry ofmetal atoms that interact with one another to form particles that grow in size. The organic solvent solvates the particles and acts as a weak capping agent to halt/slow down the growth process to a certain extent. This as-prepared colloid consists of metal nanoparticles that are quite polydisperse. In a process termed as digestive ripening, addition of a capping agent to the as-prepared colloid which is polydisperse renders it highly monodisperse either under ambient or thermal conditions. In this, as yet not well-understood process, smaller particles grow and the larger ones diminish in size until the system attains uniformity in size and a dynamic equilibrium is established. Using the SMAD method in combination with digestive ripening process, highly monodisperse metal, core-shell, alloy, and composite nanoparticles have been synthesized. This article is a review of our contributions together with some literature reports on this methodology to realize various nanostructured materials.

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