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Transition Metal Chemistry

, Volume 33, Issue 1, pp 39–53 | Cite as

A new octahedral cobalt(III) complex of (1,8)-bis(2-hydroxybenzamido)-3,6-diazaoctane incorporating phenolate-amide-amine coordination: synthesis, X-ray crystal structure, ligand substitution and redox activity with sulfur(IV) and l-ascorbic acid

  • Suprava Nayak
  • Anadi C. Dash
  • Gautam K. Lahiri
Article

Abstract

The octahedral complex, [CoIII(HL)]·9H2O (H4L = (1,8)-bis(2-hydroxybenzamido)-3,6-diazaoctane) incorporating bis carboxamido-N-, bis sec-NH, phenolate, and phenol coordination has been synthesized and characterized by analytical, NMR (1H, 13C), e.s.i.-Mass, UV–vis, i.r., and Raman spectroscopy. The formation of the complex has also been confirmed by its single crystal X-ray structure. The cyclic voltammetry of the sample in DMF ([TEAP] = 0.1 mol dm−3, TEAP = tetraethylammonium perchlorate) displayed irreversible redox processes, [CoIII(HL)] → [CoIV(HL)]+ and [CoIII(HL)] → [CoII(HL)] at 0.41 and −1.09 V (versus SCE), respectively. A slow and H+ mediated isomerisation was observed for the protonated complex, [CoIII(H2L)]+ (pK = 3.5, 25 °C, I = 0.5 mol dm−3). H2Asc was an efficient reductant for the complex and the reaction involved outer sphere mechanism; the propensity of different species for intra molecular reduction followed the sequence: [{[CoIII(HL)],(H2Asc)}–H] <<< {[CoIII(H2L)],(H2Asc)}+ < {[CoIII(HL)],(H2Asc)}. A low value (ca. 3.7 × 10−10 dm3 mol−1 s−1, 25 °C, I = 0.5 mol dm−3) for the self exchange rate constant of the couple [CoIII(HL)]/[CoII(HL)] indicated that the ligand HL3− with amido (N-) donor offers substantial stability to the CoIII state. HSO 3 and [CoIII(HL)] formed an outer sphere complex {[CoIII(HL)],(HSO 3 )}, which was slowly transformed to an inner sphere S-bonded sulfito complex, [CoIII(H2L)(HSO3)] and the latter was inert to reduction by external sulfite but underwent intramolecular SIV → CoIII electron transfer very slowly.

Keywords

Isosbestic Point Saturated Calomel Reference Electrode Outer Sphere Complex Protonation Equilibrium Data Collection Parameter 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

This work was supported by a research grant (Emeritus Scientist Scheme) awarded to A C D by the C S I R, New Delhi (Grant No 21 (0502)/01/EMR II). S N thanks the C S I R for award of a Senior Research Fellowship in this scheme. We thank Professor A K Mishra, Department of Chemistry, Indian Institute of Technology, Madras for micro analysis, and mass spectral measurements; Dr. B. B. Nayak, Dr. B Nanda, Scientists, Regional Research Laboratory, Bhubaneswar, India for Raman and NMR spectroscopy; Professor S. Mazumdar and Mr. R. K. Behera, Tata Institute of Fundamental Research, Mumbai, India for stopped flow Rapid Scan Spectral measurements and Dr. G. S. Brahma, ICFAI, Hyderabad, India for assistance

Supplementary material

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(DOC 6575 kb)

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Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  • Suprava Nayak
    • 1
  • Anadi C. Dash
    • 1
  • Gautam K. Lahiri
    • 2
  1. 1.Department of ChemistryUtkal UniversityBhubaneswarIndia
  2. 2.Department of ChemistryIndian Institute of Technology, PowaiMumbaiIndia

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