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DOI: 10.1039/A808062C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1085-1092

Mixed aza–thia crowns containing the 1,10-phenanthroline sub-unit. Substitution reactions in [NiL(MeCN)][BF4]2 {L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane}[hair space]†

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Alexander J. Blake, Jaume Casabò, Francesco A. Devillanova, Lluis Escriche, Alessandra Garau, Francesco Isaia, Vito Lippolis, Raikko Kivekas, Vincens Muns, Martin Schröder, Reijo Sillanpää and Gaetano Verani

Abstract

The substitution reactions of the co-ordinated acetonitrile molecule in [NiL(MeCN)][BF4]2 1 (L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane) with different anionic and neutral ligands L′ [Cl–, Br–, I–, CN–, SCN–, H2O, pyridine (py), aniline (an), 1,3-dimethyl-4-imidazoline-2-thione (etu) or 1,3-dimethyl-4-imidazoline-2-selone (eseu)] have been studied by using electronic spectroscopy. While the reaction with all the anionic ligands is quantitative, for the neutral ones an equilibrium takes place; the corresponding equilibrium constants have been determined in MeCN at 25 °C. The complex cations [NiL(L′)](2 – n)+ (n = 0 for neutral and 1 for anionic ligands) have also been isolated in the solid state, mainly as BF4– salts and the compounds [NiL(H2O)][ClO4]2·H2O, [NiL(Cl)]Cl·H2O, [NiL(SCN)]BF4·MeNO2, [NiL(eseu)][BF4]2 and [NiL(py)][BF4]2 have been characterized by X-ray diffraction studies. In these complexes a distorted octahedral geometry is achieved at the NiII with five sites occupied by the macrocyclic ligand L and the sixth by the appropriate ligand L′. The electrochemistry of all the prepared compounds has been studied by cyclic voltammetry. In particular the reductive cyclic voltammetry of 1 in acetonitrile shows a quasi-reversible one-electron reduction wave near 1E½ = –1.0 V vs. Fc/Fc+. Electrochemical reduction by controlled-potential electrolysis at this potential in the presence of the axial ligand PMe3 and investigation of the reduced product by ESR spectroscopy confirm the reduction process to be metal based and to correspond to the formation of the [NiIL]+ species.

References

  1. K. Wieghardt and P. Chaudhuri, Prog. Inorg. Chem., 1987, 35, 329; S. R. Cooper, Acc. Chem. Res., 1988, 21, 141 CrossRef CAS; A. J. Blake and M. Schröder, Adv. Inorg. Chem., 1990, 35, 1 CAS; C. E. Housecroft, Coord. Chem. Rev., 1992, 115, 141 CrossRef CAS; G. Reid and M. Schröder, Chem. Soc. Rev., 1990, 19, 239 RSC.
  2. A. McAuley, P. R. Norman and O. Olubuyiale, Inorg. Chem., 1984, 23, 1938 CrossRef CAS; S. Chandrasekhar and A. McAuley, Inorg. Chem., 1992, 31, 2234 CrossRef CAS and refs. Therein A. J. Blake, M. A. Halcrow and M. Schröder, J. Chem. Soc., Dalton Trans., 1992, 2803 Search PubMed; A. J. Blake, G. Reid and M. Schröder, J. Chem. Soc., Dalton Trans., 1994, 329 RSC and efs. Therein G. J. Grant, K. E. Rogers, W. N. Setzer and D. G. Van Derveer, Inorg. Chim. Acta, 1995, 234, 35 Search PubMed; C. Landgrafe and W. S. Sheldrick, J. Chem. Soc., Dalton Trans., 1996, 989 Search PubMed; M. P. Suh, K. Y. Oh, J. W. Lee and Y. Y. Boe, J. Am. Chem. Soc., 1996, 118, 777 CrossRef CAS and refs. therein.
  3. V. McKee, Adv. Inorg. Chem., 1993, 40, 323.
  4. M. M. Bishop, J. Lewis, D. O'Donoghue and P. R. Raithby, J. Chem. Soc., Chem. Commun., 1978, 476 RSC; C. W. G. Ansell, J. Lewis, M. C. Liptrot, P. R. Raithby and M. Schröder, J. Chem. Soc., Dalton Trans., 1982, 1593 RSC; C. W. G. Ansell, J. Lewis, P. R. Raithby, J. N. Ramsden and M. Schröder, J. Chem. Soc., Chem. Commun., 1982, 546 RSC; D. Parker, J. M. Lehn and J. Rimmer, J. Chem. Soc., Dalton Trans., 1985, 1517 RSC and refs. Therein P. J. Reddy, V. Ravichandran, K. K. Chacko, E. Weber and W. Saenger, Acta Crystallogr., Sect. C, 1989, 45, 1871 Search PubMed; M. E. Sobhia, K. Panneerselvam, K. K. Chacko, I.-H. Suh, E. Weber and C. Reutel, Inorg. Chim. Acta, 1992, 194, 93 CrossRef; Y.-H. Lai, L. Ma and K. Mock, Tetrahedron, 1996, 52, 4673 CrossRef CAS.
  5. C. O. D. Buchecker, J. M. Kern and J. P. Sauvage, J. Chem. Soc., Chem. Commun., 1985, 760 RSC; C. O. D. Buchecker and J. P. Sauvage, Chem. Rev., 1987, 87, 795 CrossRef CAS; C. O. D. Buchecker, J. M. Kern and J. P. Sauvage, J. Chem. Soc., Chem. Commun., 1989, 760 Search PubMed; J. P. Sauvage, Acc. Chem. Res., 1990, 23, 319 CrossRef CAS; J. C. Chambron, D. K. Mitchell and J. P. Sauvage, J. Am. Chem. Soc., 1992, 114, 4625 CrossRef CAS and refs. therein.
  6. Md. Athar Masood, R. Jagannathan and P. S. Zacharias, J. Chem. Soc., Dalton Trans., 1991, 2553 RSC; Md. Athar Masood, D. J. Hodgson and P. S. Zacharias, Inorg. Chim. Acta, 1994, 99, 221.
  7. K. J. Takeuchi, M. S. Thompson, D. W. Pipes and T. J. Meyer, Inorg. Chem., 1984, 23, 1845 CrossRef CAS; L. De Cola, F. Barigelletti, V. Balzani, P. Belser, A. von Zelewsky, F. Vögtle, F. Ebmeyer and S. Grammenudi, J. Am. Chem. Soc., 1988, 100, 7210 CrossRef; V. Balzani, F. Barigelletti and L. De Cola, Top. Curr. Chem., 1990, 158, 31 CAS; K. Bierig, R. J. Morgan, S. Tysoe, H. D. Gafney and T. C. Strekas, Inorg. Chem., 1991, 30, 4898 CrossRef; J. P. Collin, M. Baley and J. P. Sauvage, Inorg. Chim. Acta, 1991, 186, 91 CrossRef CAS; Md. Athar Masood and D. J. Hodgson, Inorg. Chem., 1993, 32, 4839 CrossRef CAS and refs. therein.
  8. J. M. Lehn, in Supramolecular Chemistry, Concepts and Perspectives, VCH, Weinheim, 1995 Search PubMed.
  9. A. J. Blake, F. Demartin, F. A. Devillanova, A. Garau, F. Isaia, V. Lippolis, M. Schröder and G. Verani, J. Chem. Soc., Dalton Trans., 1996, 3705 RSC.
  10. (a) F. Contu, F. Demartin, F. A. Devillanova, A. Garau, F. Isaia, V. Lippolis, A. Salis and G. Verani, J. Chem. Soc., Dalton Trans., 1997, 4401 RSC; (b) A. J. Blake, R. O. Gould, T. I. Hyde and M. Schröder, J. Chem. Soc., Chem. Commun., 1987, 1730, 431 RSC; (c) A. R. Brown, F. W. J. Mosselmans, S. Parsons, M. Schröder, K. J. Tayan and L. J. Yellowlees, J. Am. Chem. Soc., 1998, 120, 8805 CrossRef CAS.
  11. H. Gampp, M. Maeder, C. J. Meyer and A. Zuberbühler, Talanta, 1985, 32, 95 CrossRef CAS.
  12. G. Crisponi and V. Nurchi, J. Chem. Educ., 1989, 66, 54.
  13. S. Peng, J. A. Ibers, M. Millar and R. H. Holm, J. Am. Chem. Soc., 1976, 98, 8037 CrossRef CAS; S. Peng and V. L. Goedkin, J. Am. Chem. Soc., 1976, 98, 8500 CrossRef CAS; C. Godson, K. P. Healy and D. Pletcher, J. Chem. Soc., Dalton Trans., 1978, 972 RSC; A. Bakac and J. H. Espenson, J. Am. Chem. Soc., 1986, 108, 713 CrossRef CAS; M. S. Ram, A. Bakac and J. H. Espenson, Inorg. Chem., 1986, 25, 326.
  14. J. Lewis and M. Schröder, J. Chem. Soc., Dalton Trans., 1982, 1085 RSC.
  15. M. C. Aragoni, M. Arca, G. Crisponi and V. M. Nurchi, Anal. Chim. Acta, 1995, 316, 195 CrossRef CAS.
  16. G. M. Sheldrick, SHELXS 86–97, Programs for Crystal Structure Solution, University of Göttingen, 1986–1997.
  17. G. M. Sheldrick, SHELXL 93–97, Programs for Crystal Structure ReWnement, University of Göttingen, 1993–1997.
  18. J. Cosier and A. M. Glazer, J. Appl. Crystallogr., 1986, 19, 105 CrossRef CAS.
  19. J. A. Darr, S. R. Drake, M. B. Hursthouse and K. M. A. Malik, Inorg. Chem., 1993, 32, 5704 CrossRef CAS.
  20. W. Clegg, Acta Crystallogr., Sect. A, 1981, 37, 22 CrossRef.
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