Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Selective Synthesis of a New Macropolycycle Containing One N-CH2-N Linkage and Its Reaction with Cu2+ and Ni2+ Ions in Methanol

  • Published : 2008.10.20
Download PDF
⟨ Previous Next ⟩

Abstract

The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

Keywords

References

  1. Siegfried, L.; Comparone, A.; Neuburger, M.; Kaden, T. A. Dalton Trans. 2005, 30 and references cited therein
  2. Costamagna, J.; Ferraudi, G.; Matsuhiro, B.; Vampus-Vallette, M.; Canales, J.; Villagran, M.; Vargas, J.; Aguirre, M. J. Coord. Chem. Rev. 2000, 196, 125 https://doi.org/10.1016/S0010-8545(99)00165-4
  3. Wainwright, K. P. Coord. Chem. Rev. 1997, 166, 35 and references cited therein https://doi.org/10.1016/S0010-8545(97)00003-9
  4. Lukes, I.; Kotek, J.; Vojtisek, P.; Hermann, P. Coord. Chem. Rev. 2001, 216-217, 287
  5. Kim, K. J.; Jung, D. S.; Kim, D. S.; Choi, C. K.; Park, K. M.; Byun, J. C. Bull. Korean Chem. Soc. 2006, 27, 1747 https://doi.org/10.5012/bkcs.2006.27.11.1747
  6. Mayer, M.; Dahaoui-Gindrey, V.; Lecomte, C.; Guilard, R. Coord. Chem. Rev. 1998, 178-180, 1313 https://doi.org/10.1016/S0010-8545(98)00169-6
  7. Kang, S.-G.; Kim, M.-S.; Choi, J.-S.; Whang, D.; Kim, K. J. Chem. Soc., Dalton Trans. 1995, 363
  8. Kang, S.-G.; Nam, K.; Jeong, J. H. Inorg. Chim. Acta 2008, in press (doi:10.1016/ j.ica.2008.05.016)
  9. Kang, S.-G.; Nam, K.; Kweon, J. K.; Jung, S.-K.; Lee, U. Bull. Korean Chem. Soc. 2006, 27, 577 https://doi.org/10.5012/bkcs.2006.27.4.577
  10. Kang, S.-G.; Ryu, K. Bull. Korean Chem. Soc. 2000, 21, 535
  11. Kang, S.-G.; Ryu, K.; Song, J. Polyhedron 1999, 18, 2193 https://doi.org/10.1016/S0277-5387(99)00115-1
  12. Suh, M. P.; Choi, J.; Kang, S.-G.; Shin, W. Inorg. Chem. 1989, 28, 1763 https://doi.org/10.1021/ic00308a034
  13. Suh, M. P.; Lee, J.; Han, M. Y.; Yoon, T. S. Inorg. Chem. 1997, 36, 5651 https://doi.org/10.1021/ic970020a
  14. Tripier, R.; Lagrange, J.-M.; Espinosa, E.; Denat, F.; Guilard, R. Chem. Commun. 2001, 2278 and references cited therein
  15. Alcock, N. W.; Moore, P.; Mok, K. F. J. Chem. Soc., Perkin Trans.II 1980, 1186
  16. Comparone, A.; Kaden, T. A. Helv. Chim. Acta 1998, 81, 1765 https://doi.org/10.1002/(SICI)1522-2675(19981007)81:10<1765::AID-HLCA1765>3.0.CO;2-N
  17. Bucher, C.; Royal, G.; Barbe, J.-M.; Guilard, R. Tetrahedron Lett. 1999, 40, 2315 https://doi.org/10.1016/S0040-4039(99)00190-2
  18. Batsanov, A. S.; Goeta, A. E.; Howard, J. A. K.; Maffeo, D.; Puschmann, H.; Williams, J. A. G. Polyhedron 2001, 20, 981 https://doi.org/10.1016/S0277-5387(01)00737-9
  19. Royal, G.; Dahaoui-Gindrey, V.; Dahaoui, S.; Tabard, A.; Guilard, R.; Pullumbi, P.; Lecomte, C. Eur. J. Org. Chem. 1998, 1971
  20. Alder, R. W.; Heilbronner, E.; Honegger, E.; McEwen, A. B.; Moss, R. E.; Olefirowicz, E.; Petillo, P. A.; Sessions, R. B.; Weisman, G. R.; White, J. M.; Yang, Z.-Z. J. Am. Chem. Soc. 1993, 115, 6580 https://doi.org/10.1021/ja00068a015
  21. Kang, S.-G.; Kweon, J. K.; Lee, Y. H.; Kim, J.-S.; Lee, U. Bull. Korean Chem. Soc. 2007, 28, 489 https://doi.org/10.5012/bkcs.2007.28.3.489
  22. Kang, S.-G.; Kweon, J. K.; Jung, S.-K. Bull. Korean Chem. Soc. 1991, 12, 483
  23. Sheldrick, G. M. Acta Cryst. 2008, A64, 112
  24. Sheldrick, G. M. SADABS; University of Gottingen: Germany, 2000
  25. Suh, M. P.; Kang, S.-G. Inorg. Chem. 1988, 27, 2544 https://doi.org/10.1021/ic00287a034
  26. Kang, S.-G.; Jung, S.-K. J. Korean Chem. Soc. 1989, 33, 510
  27. Iwamoto, E.; Yokoyama, T.; Yamasaki, S.; Yabe, Y.; Kumamaru, T.; Yamamoto, Y. J. Chem. Soc., Dalton Trans. 1998, 1935
  28. Boiocchi, M.; Fabbrizzi, L.; Foti, F.; Vazquez, M. Dalton Trans. 2004, 2616

Cited by

  1. Synthesis and Characterization of New Polyaza Non-macrocyclic and Macrocyclic Nickel(II) Complexes Containing One 1,3-Diazacyclohexane Ring vol.34, pp.7, 2013, https://doi.org/10.5012/bkcs.2013.34.7.2125
  2. Synthesis and Characterization of TetraazaMacrocyclic Nickel(II) and Copper(II) Complexes Bearing Two Tetrazole Pendant Arms vol.30, pp.12, 2009, https://doi.org/10.5012/bkcs.2009.30.12.3101
  3. Synthesis and Characterization of New Tetraaza Macrocycles Bearing Two or Four N-Methoxyethyl Pendant Arms and Their Copper(II) and/or Nickel(II) Complexes vol.31, pp.9, 2010, https://doi.org/10.5012/bkcs.2010.31.9.2701
  4. Synthesis and Characterization of New Mono-N-functionalized Tetraaza Macrocyclic Nickel(II) and Copper(II) Complexes vol.32, pp.8, 2008, https://doi.org/10.5012/bkcs.2011.32.8.2565
  5. Synthesis of C-meso and/or C-racemic isomers of tetraaza macrocyclic copper(II) and nickel(II) complexes bearing one or two N-CH2OCH3 pendant arms vol.379, pp.1, 2008, https://doi.org/10.1016/j.ica.2011.09.036
  6. Synthesis of chiral cyclam analogues vol.28, pp.1, 2008, https://doi.org/10.1080/10610278.2015.1119276