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Updated: Nov 19, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
A side-on Mn(III)-peroxo supported by a non-heme pentadentate N3Py2 ligand: synthesis, characterization and
Dattaprasad D Narulkar1, Azaj Ansari2, Anil Kumar Vardhaman3
1School of Chemical Sciences, Goa University, Goa-403206, India. sndhuri@unigoa.ac.in and Department of Chemistry, Dnyanprassarak Mandal's College and Research Centre, Assagao, Goa-403507, India.
Abstract:
A mononuclear manganese(iii)-peroxo complex [MnIII(N3Py2)(O2)]+ (1a) bearing a non-heme N,N'-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)ethyl)-N'-(pyridin-2-ylmethyl)ethane-1,2-diamine (N3Py2) ligand was synthesized by the reaction of [Mn(N3Py2)(H2O)](ClO4)2 (1) with hydrogen peroxide and triethylamine in CH3CN at 25 °C. The reactivity of 1a in aldehyde deformylation using 2-phenyl propionaldehyde (2-PPA) was studied and the reaction kinetics was monitored by UV-visible spectroscopy. A kinetic isotope effect (KIE) = 1.7 was obtained in the reaction of 1a with 2-PPA and α-[D1]-PPA, suggesting nucleophilic character of 1a. The activation parameters ΔH‡ and ΔS‡ were determined using the Eyring plot while Ea was obtained from the Arrhenius equation by performing the reaction between 288 and 303 K. Hammett constants (σp) of para-substituted benzaldehydes p-X-Ph-CHO (X = Cl, F, H, and Me) were linear with a slope (ρ) = 3.0. Computational study suggested that the side-on structure of 1a is more favored over the end-on structure and facilitates the reactivity of 1a.
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