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Base hydrolysis ofcis-(methyl/ethylamine)bis(ethylenediamine) (salicylato)cobalt(III) complexes

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Summary

The kinetics of the base hydrolysis ofcis-[Co(en)2(RNH2)-(SalH)]2+ (R=Me or Et; SalH=HOC6H4CO −2 ) were investigated in aqueous ClO −4 in the 0.004–0.450 mol dm−3 [OH−] range, I=0.50 mol dm−3 at 30–40°C. The phenoxide species is hydrolysed via [OH−]-independent and [OH−]-dependent paths, the latter being first order in [OH−]. The high rate of alkali-independent hydrolysis of the phenoxide species is associated with high ΔH≠ and ΔS≠ values, in keeping with the SNICB mechanism involving an amido conjugate base generated by the phenoxide-assisted NH-deprotonation of the coordinated amine. The [OH−]-dependent path also involves the conventional SN1 CB mechanism. The rate constant, k1, for the SNICB path exhibits a steric acceleration with the increasing size of the non-labile alkylamine, whereas the rate constant, k2, for the SN1CB path shows a reverse trend.

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Authors and Affiliations

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

    Guru C. Pradhan

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  1. Guru C. Pradhan
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TMC 2578

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Pradhan, G.C. Base hydrolysis ofcis-(methyl/ethylamine)bis(ethylenediamine) (salicylato)cobalt(III) complexes. Transition Met. Chem. 17, 443–445 (1992). https://doi.org/10.1007/BF02910728

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  • DOI: https://doi.org/10.1007/BF02910728

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