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Synthesis, characterization and charge-transfer photochemistry of trans-aquo azido-N,N′-trimethylenebis(naphthylideneiminato)chromium(III)

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Abstract

A new CrIII complex, viz. trans-[Cr(naphprn)(H2O)2]ClO4·2H2O, (1) {naphprn=N,N′-trimethylenebis(naphthylideneimine)} has been synthesized and characterized. Aquo ligand substitution of ( 1 ) by the azide ligand gave rise to trans-[Cr(naphprn)(N3)(H2O)], ( 2 ). Irradiation of ( 2) in DMF gave nitrido(naphprn)chromium(V) ( 3 ). Solutions of ( 3 ) showed e.p.r. spectra at room temperature (g iso=1.9865). The i.r. spectra showed disappearance of a band at 2067cm−1 showing the breakdown of N≡N and appearance of a new band at 1074cm−1which is assigned to the Cr≡14N, stretching frequency indicating the formation of a nitrido chromium(V) complex, ( 3). The u.v.–vis. spectrum of complex ( 3 ) exhibited a d–d band maximum at 553nm (ε=120M−1cm−1). The rate of formation of ( 2 ) was found to be 5.0×10−3M−1s−1 in an aqueous acidic medium at [CrIII]=0.5×10−3M; [N3 ]=0.01–0.15M; [H+]=0.001M and I=0.2M (LiClO4). The rate of photo-decomposition of ( 2 ) to give rise to ( 3 ) was found to be 0.15×10−3s−1 in DMF.

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References

  1. 1.

    M.A.V. Riberiro da Silva, M.D.M.C. Riberiro de Silva, M.J.S. Monte, J.M. Goncalversand and E.M.R. Fernandes, J. Chem. Soc., Dalton Trans., 1257 (1997) and references therein.

  2. 2.

    R. Sriram and J.F. Endicott, Inorg. Chem., 16, 2766 (1977).

  3. 3.

    M. Katz and H.D. Gafney, Inorg. Chem., 17, 93 (1978).

  4. 4.

    K.S. Sulick and R.A. Watson, New J. Chem., 16, 633 (1992).

  5. 5.

    J.W. Buchler, C. Dreher, K.L. Lay, A. Raap and K. Gersonde, Inorg. Chem., 22, 879 (1983).

  6. 6.

    C.M. Che, Ji. X. Ma, W.T. Wang, T.F. Lai and C.K. Poon, Inorg. Chem., 27, 349 (1988); M. Faraj and C.I. Hill, J. Chem. Soc., Chem. Commun., 1487 (1989); I.B. Claudia, T.J. Collins, B.E. Maps and B.D. Santarsiern, Inorg. Chem., 25, 4322 (1986).

  7. 7.

    R.P. Farrell and P.A. Lay, Comments Inorg. Chem., 13, 133 (1992) and references therein.

  8. 8.

    C.K. Ranganathan, T. Ramasami, D. Ramaswamy and M. Santappa, Inorg. Chem., 25, 915 (1986); C.K. Ranganathan, T. Ramasami, D. Ramaswamy and M. Santappa, Inorg. Chem., 28, 1306 (1989).

  9. 9.

    B.U. Nair, M. Kanthimathi, K. Chandra Raj and T. Ramasami, Proc. Indian Acad. Sci. (Chem. Sci.), 106, 681 (1994); M. Kanthimathi, V. Subramanian and B.U. Nair, J. Indian Chem. Soc., 78, 1 (2001).

  10. 10.

    M. Kanthimathi, B.U. Nair, T. Ramasami, T. Shibahara and T. Tada, Proc. India Acad. Sci. (Chem. Sci.), 109, 235 (1997).

  11. 11.

    M. Kanthimathi, D. Jebanesan, J. Jeyakanthan and B.U. Nair, Transition Metal Chem. 27, 895 (2002).

  12. 12.

    S.I. Arshankov and A.L.Z. Poznjak, Anorg. Allg. Chem, 481, 201 (1981).

  13. 13.

    K. Meyer, J. Bendix, E. Bill, T. Weyhermuller and K. Wieghardt, Inorg. Chem., 37, 5180 (1998).

  14. 14.

    R.R. Schrick, Acc. Chem. Res., 12, 98 (1979); C.L. Hill, B.C. Schardt, J. Am. Chem. Soc., 102, 6374 (1980).

  15. 15.

    K. Dehnicke and J. Strahle, Angew. Chem., 93, 451 (1981); K. Dehnicke and J. Strahle, Angew. Chem., Int. Ed. Eng., 20, 414 (1981).

  16. 16.

    W.P. Griffith, Coord. Chem. Rev., 8, 369 (1972).

  17. 17.

    A. Hori, T. Ozawa, H. Yoshida, Y. Imori, Y. Kuribayashi, E. Nakano and N. Azuma, Inorg. Chim. Acta, 281, 207 (1998).

  18. 18.

    A. Niemann, U. Bossek, G. Haselhorst, K. Wieghardt and B. Nuber, Inorg. Chem., 35, 906 (1996).

  19. 19.

    N. Azuma, T. Ozama and T. Tsubeyama, J. Chem. Soc., Dalton Trans., 2609 (1994).

  20. 20.

    N. Azuma, Y. Imori, H. Yoshida, K. Tajima, Y. Li and J. Yamauchi, Inorg. Chim. Acta, 266, 29 (1997).

  21. 21.

    K.P. Madhusudanan, S.B. Katti, R. Vijayalakshmi and B.U. Nair, J. Mass Spectrum, 34, 880 (1999).

  22. 22.

    J.T. Groves, T. Takahashi and W.M. Butler, Inorg. Chem., 22, 884 (1983).

  23. 23.

    M. Kanthimathi, B.U. Nair, T. Ramasami, J. Jeyakanthan and D. Velmurugan, Transition Met. Chem., 25, 145 (2000).

  24. 24.

    K. Srinivasan and J.K. Kochi, Inorg. Chem., 24, 4671 (1985).

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Kanthimathi, M., Nair, B.U. Synthesis, characterization and charge-transfer photochemistry of trans-aquo azido-N,N′-trimethylenebis(naphthylideneiminato)chromium(III). Transition Metal Chemistry 29, 751–756 (2004). https://doi.org/10.1007/s11243-004-8777-y

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Keywords

  • Physical Chemistry
  • 2H2O
  • Chromium
  • Inorganic Chemistry
  • Catalysis