Skip to main content
SpringerLink
Log in

Substitution of ligands in dichloro-2-(arylazo)heterocyclepalladium(II) by 8-quinolinol: kinetics and mechanistic studies

  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Abstract

Nucleophilic substitutions of Pd(N,N′)Cl2[(N,N′ = 1-methyl-2-(arylazo)imidazole (RaaiMe), p-RC6H4N=NC3H2NN-1-Me; 2-(arylazo)pyridine (Raap), p-RC6H4N=NC5H4N; 2-(arylazo)pyrimidine (Raapm), p-RC6H4N=NC4H3N2 where R = H (a), Me (b), Cl (c)] with 8-quinolinol (HQ) have been examined by spectrophotometry at 298 K in MeCN solution. The product, Pd(Q)2, has also been confirmed by independent synthesis from Na2[PdCl4] and HQ in EtOH. The kinetics of the reaction have been studied under pseudo-first-order conditions and the analyses support a nucleophilic association path. A single phase reaction has been observed and follows the rate law, rate = a + k [Pd(N,N′)Cl2] [HQ]2. Thus, the reaction is first order in [Pd(N,N′)Cl2] and second order in [HQ]. External addition of Cl−(LiCl) suppresses the rate. The rate increases as follows: Pd(RaaiMe)Cl2 < Pd(Raap)Cl2 < Pd(Raapm)Cl2.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. B.K. Ghosh and A. Chakravorty, Coord. Chem. Rev., 95, 239 (1989); N. Bag, A. Pramanik, G.K. Lahiri and A. Chakravorty, Inorg. Chem., 31, 40 (1992); P. Ghosh, A. Pramanik, N. Bag and A. Chakravorty, J. Chem. Soc., Dalton Trans., 1883 (1992); K. Pramanik, M. Shivakumar, P. Ghosh and A. Chakravorty, Inorg. Chem., 39, 195 (2000).

    Google Scholar 

  2. B. Mondal, H. Paul, V.G. Puranik and G.K. Lahiri, J. Chem. Soc., Dalton Trans., 481 (2001).

  3. A.K. Ghosh, P. Majumdar, L.R. Falvellow, G. Mostafa and S. Goswami, Organometallics, 18, 5086 (1999); A. Saha, P. Majumder, S.-M. Peng and S. Goswami, Eur. J. Inorg. Chem., 2631 (2000).

    Google Scholar 

  4. A.H. Velders, H. Kooijman, A.L. Spek, J.G. Haasnoot, D. De Vos and J. Reedijk, Inorg. Chem., 39, 2966 (2000); A.H. Velders, F. Ugozzoli, M. Bicingi, A.M. Manetti-Lanfredi, J.G. Haasnoot and J. Reedijk, Inorg. Chem., 39, 3838 (2000).

    Google Scholar 

  5. K.S.Y. Leung and Y. Li, Inorg. Chem. Commun., 2, 599 (1999); V.W.W. Yam, V.C.Y. Lan and L.X. Wu, J. Chem. Soc.,Dalton Trans., 1461 (1998); F.S. Kong and W.T. Wong, J. Organometal. Chem., 589, 180 (1999); Q.E. Cao and Z.D. Hu, Indian J. Chem., 37A, 1029 (1998); M.M. Shoukry, E.M. Khiary and W.F. Elshazly, Synth. React. Inorg. Met.-Org. chem., 27, 737 (1997); J. Griffiths and C.J. Riepl, Chem. Commun., 1349 (1998); T. Yutaka, M. Kurihara, K. Kubo and H. Nishihara, Inorg. Chem., 39, 3438 (2000).

    Google Scholar 

  6. T.K. Misra, D. Das and C. Sinha, Polyhedron, 16, 4163 (1997); P.K. Santra, D. Das, T.K. Misra, R. Roy, C. Sinha and S.-M. Peng, Polyhedron, 18, 1909 (1999).

    Google Scholar 

  7. T.K. Misra, D. Das, C. Sinha, P.K. Ghosh and C.K. Pal, Inorg. Chem., 37, 1672 (1998); P. Byabartta, P.K. Santra, T.K. Misra, C. Sinha and C.H.L. Kennard, Polyhedron, 20, 905 (2001); P.K. Santra, T.K. Misra, D. Das, C. Sinha, A.M.Z. Slawin and J.D. Woollins, Polyhedron, 18, 2869 (1999).

    Google Scholar 

  8. S. Pal, T.K. Misra, P. Chattopadhyay and C. Sinha, Proc. Indian Acad. Sci (Chem. Sci.), 111, 687 (1999); P. Byabartta, S. Pal, T.K. Misra, C. Sinha, F.-L. Liao, K. Panneerselvam and T.-H. Lu, J. Coord. Chem., 55, 479 (2002); S. Senapati, U.S. Ray, P.K. Santra, C. Sinha, J.D. Woollins and A.M.Z. Slawin, Polyhedron, 21, 753 (2002).

    Google Scholar 

  9. R. Roy, P. Chattopadhyay, C. Sinha and S. Chattopadhyay, Polyhedron, 15, 3361 (1996); D. Das, M.K. Nayak and C. Sinha, Transition Met. Chem., 22, 172 (1997); D. Das and C. Sinha, Transition Met. Chem., 23, 309 (1998).

    Google Scholar 

  10. S. Pal, D. Das, P. Chattopadhyay, C. Sinha, K. Panneerselvam and T.-H. Lu, Polyhedron, 19, 1263 (2000); G.K. Routh, S. Pal, D. Das, C. Sinha, A.M.Z. Slawin and J.D. Woollins, Polyhedron, 20, 363 (2001).

    Google Scholar 

  11. P.K. Santra, U.S. Ray, S. Pal and C. Sinha, Inorg. Chem. Commun., 4, 269 (2001).

    Google Scholar 

  12. J.K. Nag, P.K. Santra, C. Sinha, F.-L. Liao and T.-H. Lu, Polyhedron, 20, 2253 (2001).

    Google Scholar 

  13. D. Das, A.K. Das and C. Sinha, Talanta, 48, 1013 (1999); D. Das, A.K. Das and C. Sinha, Anal Lett., 32, 567 (1999).

    Google Scholar 

  14. C.K. Pal, S. Chattapadhyay, C. Sinha, D. Bandyopadhyay and A. Chakravorty, Polyhedron, 13, 999 (1994); P.K. Santra, R. Ray and C. Sinha, Proc. Indian Acad. Sci. (Chem. Sci.), 112, 523 (2000).

    Google Scholar 

  15. P.K. Santra, P. Byabartta, S. Chattopadhyay, L.R. Falvello and C. Sinha, Eur. J. Inorg. Chem., 1124 (2002); S. Senapoti, P.K. Santra and C. Sinha, Transition Met. Chem., in press.

  16. B.K. Santra, G.A. Thakur, P. Ghosh, K. Pramanik and G.K. Lahiri, Inorg. Chem., 35, 3050 (1996); B.K. Santra and G.K. Lahiri, J. Chem. Soc., Dalton Trans, 1883 (1997).

    Google Scholar 

  17. R. Roy, T.K. Misra, C. Sinha, A. Mahapatra and A. Samyal, Transition Met. Chem., 22, 453 (1997); R. Roy, D. Das, M. Banerjee, C. Sinha and A. Mahapatra, Transition Met. Chem., 26, 205 (2001).

    Google Scholar 

  18. G.K. Rauth, D. Das, C. Sinha, K. Bag and A. Mahapatra, Transition Met. Chem., 27, 639 (2002).

    Google Scholar 

  19. G.K. Rauth, S.K. Jasimmudin, A. Mahapatra and C. Sinha, Inorg. React. Mech., in press.

  20. R. Roy, D. Das, A. Mahapatra and C. Sinha, Inorg. React. Mech., 2, 213 (2000).

    Google Scholar 

  21. V. Alexeyev, Quantitative Analysis, FLPH, Moscow, 1964, p. 130; A.I. Vogel, Quantitative Inorganic Analysis, ELBS, London, 1975, p. 387.

    Google Scholar 

  22. F. Basalo and R.G. Pearson, Mechanism of Inorganic Reactions. A Study of Metal complexes in Solution, 2nd edit. Wiley, New York, 1967; R.G. Wilkins, Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd edit. VCH, Weinheim, 1991.

    Google Scholar 

  23. C. Sinha, Ph.D. Thesis, Jadavpur University, Kolkata-32, India, 1990.

    Google Scholar 

  24. G.K. Rauth, S. Pal, D. Das, C. Sinha, A.M.Z. Slawin and J.D. Woollins, Polyhedron, 20, 363 (2001).

    Google Scholar 

  25. S. Pal, D. Das, P. Chattopadhyay, C. Sinha, K. Panneerselvam and T.-H. Lu, Polyhedron, 19, 1263 (2000); J. Arpalahli, P. Lehikoinen, Inorg. Chem., 29, 2564 (1990).

    Google Scholar 

  26. E.C. Constable, Coord. Chem. Rev., 93, 205 (1989).

    Google Scholar 

  27. P.S. Sengupta, R. Sinha and G.S. De, Indian J. Chem., 40A, 509 (2001).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Burdwan, Burdwan, 713104, India

    Goutam K. Rauth, Subrata Maity & Chittaranjan Sinha

  2. Department of Chemistry, University of Kalyani, Kalyani, 741235, India

    Ambikesh Mahapatra

Authors
  1. Goutam K. Rauth
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Subrata Maity
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chittaranjan Sinha
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ambikesh Mahapatra
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rauth, G.K., Maity, S., Sinha, C. et al. Substitution of ligands in dichloro-2-(arylazo)heterocyclepalladium(II) by 8-quinolinol: kinetics and mechanistic studies. Transition Metal Chemistry 28, 518–524 (2003). https://doi.org/10.1023/A:1025068620012

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1025068620012

Keywords

Search

Navigation