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Kinetics of oxidation of glutathione by an octahedral cobalt(III) complex with phenolate–amide–amine coordination

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Abstract

The reduction of the octahedral cobalt(III) complex CoIII(HL)·9H2O, H4L = 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane by glutathione (GSH) has been studied by conventional spectrophotometry at 25.0 ≤ t/°C ≤ 45.0, 0.02 ≤ [H+]/mol dm−3 ≤ 0.20 and I = 0.3 mol dm−3 (NaClO4). The reaction is biphasic. The fast initial phase is attributed to the H+-induced formation of the mixed ligand complex, [CoIII(H2L)GSH]+, for which the rate-limiting step is the chelate ring opening via CoIII–NH (amide–N) bond cleavage of the protonated species, [CoIII(H2L)]+. Outer-sphere association equilibria between GSH/GSH2 + and [CoIII(H2L)]+ substantially retard the ring opening process and consequently the mixed ligand complex formation. This is then followed by a slow phase involving reduction of [CoIII(H2L)GSH]+ by both GSH and GSH2 +. The final products are the corresponding Co(II) complex and the oxidized form of GSH, GS–SG. The kinetic data and activation parameters for the redox process are interpreted in terms of an outer-sphere electron transfer mechanism.

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Acknowledgments

The financial assistance from the University Grants Commission (UGC), New Delhi, through a Dr D. S. Kothari postdoctoral fellowship (Scheme No. F4-2/2006(BSR)/13-47/2007(BSR)) to S.N. is gratefully acknowledged. The authors thank Dr. Achyutananda Acharya, College of Engineering and Technology, Bhubaneswar, India, and Mr. Akshaya K. Kar, teacher fellow, Department of Chemistry, Utkal University for assistance.

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  1. Suprava Nayak

    Present address: Department of Chemistry, CMR Institute of Technology, Kandlakoya, Hyderabad, India

Authors and Affiliations

  1. Department of Chemistry, Osmania University, Hyderabad, 500007, India

    Suprava Nayak & K. Venugopal Reddy

  2. Department of Chemistry, Utkal University, Bhubaneswar, 751004, India

    Anadi C. Dash

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  1. Suprava Nayak
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  2. K. Venugopal Reddy
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  3. Anadi C. Dash
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Correspondence to Suprava Nayak.

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Nayak, S., Reddy, K.V. & Dash, A.C. Kinetics of oxidation of glutathione by an octahedral cobalt(III) complex with phenolate–amide–amine coordination. Transition Met Chem 39, 177–187 (2014). https://doi.org/10.1007/s11243-013-9787-4

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