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Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes

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Summary

The reaction of (αβ)-(tetren)CoOH2+ with S2O 2-3 in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH2+,S2O 2-3 ] formation. Replacement of coordinated OH- by S2O 2-3 is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH2+⇌ (tetren-H)CoOH 2+2 , the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.

In acid medium the S-bonded (tetren)Co(S2O3)+ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS2O3]+ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S2O 2-3 .

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Authors and Affiliations

  1. Department of Chemistry, M.P.C. College, 757 001, Orissa, India

    Rita Das

  2. Regional Research Laboratory, 751 013, Orissa, India

    Nigamananda Das

  3. Department of Chemistry, Utkal University, 751 004, Orissa, India

    Anadi C. Dash

  4. Department of Applied Chemistry, University College of Science and Technology, Calcutta University, 700 009, Calcutta, India

    Ansuman Roy & Shyamal K. Sarkar

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  1. Rita Das
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  2. Nigamananda Das
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  3. Anadi C. Dash
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  4. Ansuman Roy
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  5. Shyamal K. Sarkar
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Das, R., Das, N., Dash, A.C. et al. Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes. Transition Met Chem 21, 90–94 (1996). https://doi.org/10.1007/BF00166022

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