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Ligand control on the reactions of oxygen- and sulphur-bonded (sulphito)pentaminecobalt(III) complexes in solution

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Abstract

The kinetics of formation, acid-catalysed aquation, ligand isomerisation (CoIIIOSO2+→CoIIISO3+), intramolecular electron-transfer, and base-catalysed hydrolysis and isomerisation of O-bonded sulphito complexes, cis-[Co(en)2(B)(OSO2–O)]+[B=benzimidazole (bzimH), N-methylimidazole (N-meim)] and the anation of cis-[Co(en)2(B)OH)]2+ [B=bzimH, N-meim and imH (imidazole)] by oxSO2−3 are reported. Steric acceleration is observed in the formation and acid-catalysed aquation of the O-sulphito complexes. The ligand isomerisation leads to loss of the monodentate amine with the formation of trans-[Co(en)2(SO3–S)2]− (in an excess of sulphite). Steric acceleration is more pronounced in the isomerisation and base hydrolysis than in the redox process. The results indicate cis labilisation of the coordinated O-sulphite.

The [(tetraethylenepentamine)Co(OSO2–O)]+ cation undergoes base hydrolysis 103 times faster than the corresponding (en)2(B) complexes; base-catalysed ligand isomerisation for the former is not observed unlike in the latter. The anation of cis-[Co(en)2(B)OH]2+ (B=imH, bzimH, N-meim) by SO2−3 in a mild alkali pH range (pH=7.9–9.6) and in an excess of SO2−3, yields exclusively trans-[Co(en)2(SO3–S)2]− with no evidence for the formation of the cis-[Co(en)2(B)(SO3–S)]+ or its O-sulphito analogue. The intramolecularly generated amido conjugate base of the sulphite ion-pair, {cis-[Co(en)2(B)OH]2+,SO32−}.41cm{cis-[Co(en)(en-H) (B)- OH2]2+,SO32−}, is believed to generate a five-coordinate intermediate (TBP) that captures the S-end of SO2−3 selectively from a site trans-to the amine B so that the amine is labilised by the trans effect of the sulphite. The NH-deprotonated coordinated imidazolate or benzimidazolate species, cis-[Co(en)2(bzm/im)OH]+, do not undergo anation by SO2−3.

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Authors and Affiliations

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

    Anadi C. Dash, Ajay K. Patnaik & Achyuta N. Acharya

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  1. Anadi C. Dash
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  2. Ajay K. Patnaik
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  3. Achyuta N. Acharya
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Dash, A.C., Patnaik, A.K. & Acharya, A.N. Ligand control on the reactions of oxygen- and sulphur-bonded (sulphito)pentaminecobalt(III) complexes in solution. Transition Metal Chemistry 23, 45–55 (1997). https://doi.org/10.1023/A:1006901900302

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