Synthesis 2006(9): 1504-1512  
DOI: 10.1055/s-2006-926439
PAPER
© Georg Thieme Verlag Stuttgart · New York

New Ditopic and Tripodal 1,2,4-Triazole- and Tetrazole-Based Ligands for Coordination Chemistry

Yves Bolanda, Pascale Hertsensa, Jacqueline Marchand-Brynaertb, Yann Garcia*a
a Unité de Chimie des Matériaux Inorganiques et Organiques, Département de Chimie, Faculté des Sciences, Université catholique de Louvain­, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium
b Unité de Chimie Organique et Médicinale, Département de Chimie, Faculté des Sciences, Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Fax: +32(10)472831; e-Mail: garcia@chim.ucl.ac.be;
Further Information

Publication History

Received 12 October 2005
Publication Date:
11 April 2006 (eFirst)

Abstract

The practical synthesis of two new classes of polytopic azole-based ligands is reported. The synthesis of the precursor amines was achieved by substitution of a leaving group by an azide followed by reduction with triphenylphosphine and water. Another efficient method employs a Mitsunobu coupling with phthalimide allowing the conversion of a primary alcohol into a primary amine. The triazole and tetrazole were obtained by cyclization of these amine precursors. The first family consisted of ditopic ligands containing both 1-R-tetrazole and 4-R-1,2,4-triazole moieties linked by an alkyl spacer, while the second consists of branched ligands with three azole cycles linked to a benzene core through ether bonds. Both classes are suitable for building multidimensional polynuclear coordination assemblies and for the observation of thermal spin state crossover behavior with iron(II) ions.

    References

  • 1 Buechel KH. ACS Symposium Series, Vol. 304   American Chemical Society; Washington DC: 1986. 
  • 2 Bergthaller P. Imaging Sci. J.  2002,  50:  187 
  • 3 Meister RT. In Chemical Handbooks ’92   Meister Publishing Company; Willoughby OH: 1992. 
  • 4 Hammerl A. Klapoetke TM. Noeth H. Warchhold M. Holl G. Kaiser M. Ticmanis U. Inorg. Chem.  2001,  40:  3570 
  • 5 Bayer HO, Cook RS, and von Meyer WC. inventors; US Patent  3821376.  1974
  • 6 Seidel L, Von Meyer WC, and Greenfield S. inventors; US Patent  4120684.  1978
  • 7 Klingele MH. Brooker S. Coord. Chem. Rev.  2003,  241:  119 
  • 8a Haasnoot JG. In Magnetism: A Supramolecular Function   Kahn O. Kluwer Academic Publishers; Dordrecht: 1996.  p.299 
  • 8b Haasnoot JG. Coord. Chem. Rev.  2000,  200/202:  131 
  • 9 Inoue M. Kubo M. Coord. Chem. Rev.  1976,  21: 
  • 10 Beckmann U. Brooker S. Coord. Chem. Rev.  2003,  245:  17 
  • 11 Lees AC. Evrard B. Keyes TE. Vos JG. Kleverlaan CJ. Alebbi M. Bignozzi CA. Eur. J. Inorg. Chem.  1999,  2309 
  • 12 Garcia Y. Niel V. Muñoz MC. Real JA. Top. Curr. Chem.  2004,  233:  229 
  • 13 Gütlich P. Garcia Y. Spiering H. In Magnetism: From Molecules to Materials   Vol. IV:  Miller JS. Drillon M. Wiley-VCH; Weinhem: 2003.  p.271 
  • 14 Kahn O. Kröber J. Jay C. Adv. Mater.  1992,  4:  718 
  • 15 Garcia Y. Kahn O. Rabardel L. Chansou B. Salmon L. Tuchagues J.-P. Inorg. Chem.  1999,  38:  4663 
  • 16 Bronisz R. PhD Thesis   University of Wroclaw; Poland: 1999. 
  • 17 van Koningsbruggen PJ. Garcia Y. Bravic G. Chasseau D. Kahn O. Inorg. Chim. Acta  2001,  326:  101 
  • 18a van Koningsbruggen PJ. Garcia Y. Kahn O. Fournès L. Kooijman H. Spek AL. Haasnoot JG. Moscovici J. Provost K. Michalowicz A. Renz F. Gütlich P. Inorg. Chem.  2000,  39:  1891 
  • 18b van Koningsbruggen PJ. Garcia Y. Kooijman H. Spek AL. Haasnoot JG. Kahn O. Linares J. Codjovi E. Varret F. J. Chem. Soc., Dalton Trans.  2001,  466 
  • 18c Schweifer J. Weinberger P. Mereiter K. Boca M. Reichl C. Wiesinger G. Hilscher G. van Koningsbruggen PJ. Kooijman H. Grunert M. Linert W. Inorg. Chim. Acta  2002,  339:  297 
  • 18d Grunert CM. Schweifer J. Weinberger P. Linert W. Mereiter K. Hilscher G. Muller M. Wiesinger G. van Koningsbruggen PJ. Inorg. Chem.  2004,  43:  155 
  • 18e Muttenthaler M. Bartel M. Weinberger P. Hilscher G. Linert W. J. Mol. Struct.  2005,  741:  159 
  • 19 Garcia Y. van Koningsbruggen PJ. Kooijman H. Spek AL. Haasnoot JG. Kahn O. Eur. J. Inorg. Chem.  2000,  307 ; see also corrigendum on page 575
  • 20 Gaponik PN. Karavai VP. Grigor’ev YuV. Chem. Heterocycl. Compd. (Engl. Transl.)  1985,  21:  1521 
  • 21 Janiak C. J. Chem. Soc., Chem. Commun.  1994,  545 
  • 22 Bronisz R. Ciunik Z. Drabent K. Rudolf MF. Conference Proceedings, ICAME 1996  1996,  50:  15 
  • 23 Lemercier G. Verelst M. Bousseksou A. Varret F. Tuchagues J.-P. In Magnetism: A Supramolecular Function   Kahn O. Kluwer Academic Publishers; Dordrecht: 1996.  p.335 
  • 24 Long GJ. Grandjean F. Reger DL. Top. Curr. Chem.  2004,  233:  91 
  • 25 Asratyan GV. Attaryan OS. Pogosyan AS. Eliazyan GA. Darbinyan EG. Matsoyan SG. J. Appl. Chem. USSR (Engl. Transl.)  1986,  59:  1202 
  • 26 Kamiya T, and Saito Y. inventors; US Patent  3767667.  1973
  • 27 Lakanen JR. Coward JK. Pegg AE. J. Med. Chem.  1992,  35:  724 
  • 28 Garcia Y. Ksenofontov V. Levchenko G. Gütlich P. J. Mater. Chem.  2000,  10:  2274 
  • 29 Mitsunobu O. Synthesis  1981, 
  • 30 Curtis WD. Stoddart JF. Jones GH. J. Chem. Soc., Perkin Trans. 1  1977,  785 
  • 31 Nithyanandhan J. Jayaraman N. J. Org. Chem.  2002,  67:  6282 
  • 32 Defacqz N. Van T T. Cordi A. Marchand-Brynaert J. Tetrahedron Lett.  2003,  44:  9111 
  • 33 Lavrenova LG. Ikorskii VN. Varnek VA. Oglezneva IM. Larionov SV. Koord. Khim.  1986,  12:  207 
  • 34 Carlin RL. van Duyneveldt AJ. Magnetic Properties of Transition Metal Compounds   Springer-Verlag; Berlin: 1977. 
  • 35 Kahn O. Molecular Magnetism   Wiley-VCH; Weinhem: 1993. 
  • 36 Gaponik PN. Karavai VP. Chem. Heterocycl. Compd. (Engl. Transl.)  1985,  21:  1172 
  • 37 Fujigaya T. Jiang D.-L. Aida T. J. Am. Chem. Soc.  2005,  127:  5484 
  • 38 Lagarec K. Rancourt DG. Recoil Mössbauer Spectral Analysis Software for Windows 1.0   Department of Physics, University of Ottawa; Canada: 1998. 
  • 39 Helferich B. Schirp H. Chem. Ber.  1951,  84:  469