Cp*Rh(III) complexes 1a and 1b (Cp* = 1, 2, 3, 4, 5-pentamethylcyclopentadienyl) having functional N,O chelate ligands have been synthesized and characterized by H-1, C-13{H-1} NMR spectroscopy, elemental analysis, IR spectroscopy and X-ray diffraction. Reactivity of these complexes has been investigated towards dehydrogenation of alcohols and hydrogenation of ketones. It was found that these compounds are precursors to the formation of Rh nanoparticles which serve as catalysts, as evidenced by mercury poisoning of the catalysis and direct observation of the particles by TEM, EDX, and XRD. (C) 2017 Elsevier B.V. All rights reserved.