Anadi C Dash
Articles written in Journal of Chemical Sciences
Volume 106 Issue 3 June 1994 pp 808-808
Volume 116 Issue 3 May 2004 pp 133-142
An O-bonded sulphito complex, Rh(OH2)5(OSO2H)2+, is reversibly formed in the stoppedflow time scale when Rh(OH2)63+ and SO2/HSO3− buffer (1 <pH< 3) are allowed to react. For Rh(OH2)5OH2++ SO2 □ Rh(OH2)5(OSO2H)2+ (k1/k-1), k1 = (2.2 ±0.2) × 103 dm3 mol−1 s−1, k−1 = 0.58 ±0.16 s−1 (25°C,
Volume 123 Issue 4 July 2011 pp 497-507
The
Volume 126 Issue 3 May 2014 pp 547-559 Regular Articles
Akshaya K Kar Achyutananda Acharya Guru C Pradhan Anadi C Dash
The kinetics of oxidation of glyoxylic acid (HGl) by MnIII(salen)(OH2)$^+_2$ ((H2salen = N,N'- bis(salicylidene)ethane-1,2-diamine) is investigated at 30.0-45.0°C, 1.83 ≤ pH ≤ 6.10, I = 0.3 mol dm-3(NaClO4). The products are identified as formic acid, CO2 and MnII with the reaction stoichiometry, |𝛥[MnIII]/𝛥[HGl]| = 2. The overall reaction involves fast equilibrium pre-association of MnIII(salen)(OH2)$^+_2$ with HGl and its conjugate base Gl− forming the corresponding inner sphere complexes (both HGl and Gl− being the monohydrate gem-diol forms) followed by the slow electron transfer steps. In addition, the second order electron transfer reactions involving the inner-sphere complexes and HGl/Gl− are also observed. The rate, equilibrium constants and activation parameters for various steps are presented. MnIII(salen)(OH2)(Gl) is virtually inert to intra molecular electron transfer while the process is facile for MnIII(salen)(OH2)(HGl)+ (10$^5k_{et} = 2.8 \pm 0.3$ s-1 at 35.0°C) reflecting the involvement of proton coupled electron transfer mechanism in the latter case. A computational study of the structure optimization of the complexes, trans-MnIII(salen)(OH2)$^+_2$, trans-MnIII(salen)(OH2)(Gl), and
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