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DOI: 10.1039/A803517B (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1998, 94, 2769-2774

Kinetically hindered reaction of bis(2,2′-bipyridine) chloro and thiocyanato-N nickel(II) complexes with 2,2′-bipyridine in N,N-dimethylformamide

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Morito Komiya, You Kobayashi, Hideki Meno and Shin-ichi Ishiguro

Abstract

Reaction kinetics of bis(2,2′-bipyridine) chloro and thiocyanato-N nickel(II) complexes with 2,2′-bipyridine (bipy) have been studied in N,N-dimethylformamide (DMF) by spectrophotometry at 298 K. The rate constant kf0 of 37.2 mol-1 d s-1 for [Ni(bipy-N,N)2]2++bipy→[Ni(bipy-N,N)3]2+ is obtained. Interestingly, it is found that the corresponding apparent rate of formation kf of [Ni(bipy-N,N)3]2+ in solution containing chloride or thiocyanate ions is significantly smaller than kf0. In solution containing these anions, the [NiX(bipy-N,N)2]+ and [NiX2(bipy-N,N)2] (X=Cl or NCS) complexes are extensively formed, and their formation constants and individual electronic spectra have been determined. The kf of [Ni(bipy-N,N)3]2+ was thus analysed by considering the formation of these ternary complexes in equilibrium, and the intrinsic rate constants kf1 and kf2 for the reactions [NiX(bipy-N,N)2]++bipy→[Ni(bipy-N,N)3]2++X- and [NiX2(bipy-N,N)2]+bipy→[Ni(bipy-N,N)3]2++2X-, respectively, have been obtained. The kf1 and kf2 values thus obtained are significantly smaller than kf0, implying that these reaction pathways are strongly hindered. The formation of [Ni(bipy-N,N)3]2+ may proceed through either [Ni(bipy-N,N)2(bipy-N)S]2+ or [NiX(bipy-N,N)2(bipy-N)]+ as the intermediate, where bipy-N denotes a unidentately coordinating 2,2′-bipyridine and S the solvent. The kinetic results suggest that the pathway through the intermediate [NiX(bipy-N,N)2(bipy-N)]+ is unusually suppressed, probably due to strong intramolecular ligand–ligand interaction between a unidentately coordinating 2,2′-bipyridine and the anion.

References

  1. S. Ishiguro, L. Nagy and H. Ohtaki, Bull. Chem. Soc. Jpn., 1987, 60, 2053 CAS.
  2. S. Ishiguro, L. Nagy and H. Ohtaki, Bull. Chem. Soc. Jpn., 1987, 60, 2865 CAS.
  3. S. Ishiguro, K. Ozutsumi, L. Nagy and H. Ohtaki, J. Chem. Soc., Dalton Trans., 1989, 655 RSC.
  4. S. Ishiguro and K. Ozutsumi, Bull. Chem. Soc. Jpn., 1989, 62, 2392 CAS.
  5. S. Ishiguro, K. Ozutsumi, M. Miyauchi and H. Ohtaki, Inorg. Chem., 1989, 28, 3258 CrossRef CAS.
  6. S. Ishiguro, K. Ozutsumi and A. Ohtaki, Bull. Chem. Soc. Jpn., 1990, 63, 3030 CAS.
  7. S. Ishiguro, M. Miyauchi and K. Ozutsumi, J. Chem. Soc., Dalton Trans., 1990, 2035 RSC.
  8. M. Komiya, S. Yoshida and S. Ishiguro, J. Solution Chem., 1997, 26, 997 CAS.
  9. R. G. Wilkins, Acc. Chem. Res., 1970, 3, 408 CrossRef CAS.
  10. D. J. Hewkin and R. H. Prince, Co-ordin. Chem. Rev., 1970, 5, 45 Search PubMed.
  11. K. Kustin and J. Swinehart, Prog. Inorg. Chem., 1970, 13, 107 CAS.
  12. R. H. Holyer, C. D. Hubbard, S. F. A. Kettle and R. G. Wilkins, Inorg. Chem., 1965, 4, 929 CrossRef CAS.
  13. R. H. Holyer, C. D. Hubbard, S. F. A. Kettle and R. G. Wilkins, Inorg. Chem., 1966, 5, 622 CrossRef CAS.
  14. H. P. Bennetto and E. F. Caldin, J. Chem. Soc. A, 1971, 2191, 2198 RSC.
  15. D. J. Benton and P. Moore, J. Chem. Soc., Chem. Commun., 1972, 717 RSC; J. Chem. Soc., Dalton Trans., 1972, 399 Search PubMed.
  16. P. Moore and D. M. W. Buck, J. Chem. Soc., Dalton Trans., 1973, 1602 RSC.
  17. D. M. W. Buck and P. Moore, J. Chem. Soc., Chem. Commun., 1974, 60 RSC.
  18. D. M. W. Buck and P. Moore, J. Chem. Soc., Dalton Trans., 1974, 2082 RSC.
  19. P. K. Chattopadhyay and J. F. Coerzee, Inorg. Chem., 1973, 12, 113 CrossRef CAS.
  20. A. M. Jasceanu and P. Moore, J. Chem. Soc., Dalton Trans., 1998, 369 RSC.
  21. P. A. Cock, C. E. Cottrell and R. K. Boyd, Can. J. Chem., 1972, 50, 402 CAS.
  22. P. K. Chattopadhyay and J. F. Coerzee, Inorg. Chem., 1976, 15, 400 CrossRef CAS.
  23. J. F. Coetzee, Pure Appl. Chem., 1977, 49, 27 CAS.
  24. S. Ishiguro and K. Ozutsumi, Inorg. Chem., 1990, 29, 1117 CrossRef CAS.
  25. N. A. Matwiyoff, Inorg. Chem., 1966, 5, 788 CrossRef CAS.
  26. J. S. Babiec, C. H. Langford and T. R. Stengle, Inorg. Chem., 1966, 5, 1362 CrossRef CAS.
  27. Z. Luz, J. Chem. Phys., 1969, 51, 1206 CAS.
  28. M. Eigen, Z. Phys. Chem., 1954, (Frankfurt am Main), 1, 176 Search PubMed.
  29. R. M. Fuoss, J. Am. Chem. Soc., 1958, 80, 5059 CrossRef CAS.
  30. C. T. Lin and D. B. Rorabacher, Inorg. Chem., 1973, 12, 2402 CrossRef CAS.
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