![Sample our Physical Sciences journals, sign in here to start your FREE access for 14 days]({"type":"image" , "src" : "/sda/110819/TOC-Subject-Sample-2021-Physical-Sciences.jpg"})
Abstract
Phenylhydrazine (R) quantitatively reduces [Fe2(μ-O)(phen)4(H2O)2]4+ (1) (phen = 1,10-phenanthroline) and its conjugate base [Fe2(μ-O)(phen)4(H2O)(OH)]3+ (2) to [Fe(phen)3]2+ in presence of excess 1,10-phenanthroline in the pH range 4.12–5.55. Oxidation products of phenylhydrazine are dinitrogen and phenol. The reaction proceeds through two parallel paths: 1 + R → products (k 1), 2 + R → products (k 2); neither RH+ nor the doubly deprotonated conjugate base of the oxidant, [Fe2(μ-O)(phen)4(OH)2]2+ (3) is kinetically reactive though both are present in the reaction media. At 25.0°C, I = 1.0 M (NaNO3), the rate constants are k 1 = 425 ± 10 M−1 s−1 and k 2 = 103 ± 5 M−1 s−1. An inner-sphere, one-electron, rate-limiting step is proposed.
Acknowledgements
This work was financially supported by the Council of Scientific and Industrial Research, New Delhi (India). We gratefully acknowledge Dr. Joydeep Mukherjee, Lecturer, Environmental Science Programme of Jadavpur University for HPLC measurements.