Skip to main content
SpringerLink
Log in

Silver complexes of 1,2,4-triazole derived N-heterocyclic carbenes: Synthesis, structure and reactivity studies

  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Two silver(I) complexes {[1-R-4-(N-t-butylacetamido)-1,2,4-triazol-5-ylidene]2Ag} +  Cl −  [R = Et (1b), i-Pr (2b)] of N/O-functionalized N-heterocyclic carbenes derived from 1,2,4-triazoles are reported. The silver complexes, 1b and 2b, have been synthesized from the reaction of the N/O-functionalized triazolium chloride salts namely, 1-R-4-(N-t-butylacetamido)-1,2,4-triazolium chloride [R = Et (1a), i-Pr (2a)] by treatment with Ag2O in 53–56% yield. The 1,2,4-triazolium chloride salts 1a and 2a were prepared by the alkylation reaction of 1-R-1,2,4-triazole (R = Et, i-Pr) with N-t-butyl-2-chloro acetamide in 47–63% yield. The molecular structures of the silver(I) complexes, 1b and 2b, have been determined by X-ray diffraction studies. The density functional theory studies on the silver 1b and 2b complexes suggest that the 1,2,4-triazole derived N-heterocyclic carbenes to be strong σ −donating ligands similar to the now much recognized imidazole-based N-heterocyclic carbenes. The reactivity studies with (SMe2)AuCl and (SMe2)CuBr indicated the silver complexes, 1b and 2b, to be good transmetallating agents.

A rare series of silver(I) complexes of 1,2,4-triazole-based N/O-functionalized N-heterocyclic carbenes were designed with their intended use as transmetallating agents.

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. (a) Pugh D and Danopoulos A A 2007 Coord. Chem. Rev. 251 610; (b) Crudden C M and Allen D P 2004 Coord. Chem. Rev. 248 2247; (c) Peris E and Crabtree R H 2004 Coord. Chem. Rev. 248 2239; (d) Herrmann W A 2002 Angew. Chem. Int. Ed. 41 1290

  2. Yen S K, Koh L L, Hahn F E, Huynh H V and Hor T S A 2006 Organometallics 25 5105

    Article  CAS  Google Scholar 

  3. (a) Zanardi A, Mata J A and Peris E 2009 Organometallics 28 4335; (b) Ros A, Alcarazo M, Iglesias-Sigüenza J, Díez E, Álvarez E, Fernández R and Lassaletta J M 2008 Organometallics 27 4555; (c) Gnanamgari D, Moores A, Rajaseelan E and Crabtree R H 2007 Organometallics 26 1226

  4. Mathew P, Neels A and Albrecht M 2008 J. Am. Chem. Soc. 130 13534

    Article  CAS  Google Scholar 

  5. Schütz J, Herdtweck E and Herrmann W A 2004 Organometallics 23 6084

    Article  Google Scholar 

  6. (a) Samantaray M K, Pang K, Shaikh M M and Ghosh P 2008 Dalton Trans. 4893; (b) Samantaray M K, Pang K, Shaikh M M and Ghosh P 2008 Inorg. Chem. 47 4153; (c) Ray L, Shaikh M M and Ghosh P 2008 Inorg. Chem. 47 230; (d) Samantaray M K, Roy D, Patra A, Stephen R, Saikh M, Sunoj R B and Ghosh P 2006 J. Organomet. Chem. 691 3797

  7. (a) John A and Ghosh P 2010 Dalton Trans. 39 7183; (b) Ray S, Mohan R, Singh J K, Samantaray M K, Shaikh M M, Panda D and Ghosh P 2007 J. Am. Chem. Soc. 129 15042; (c) Ray S, Asthana J, Tanski J M, Shaikh M M, Panda D and Ghosh P 2009 J. Organomet. Chem. 694 2328

  8. (a) Kumar S, Shaikh M M and Ghosh P 2009 J. Organomet. Chem. 694 4162; (b) Ray L, Shaikh M M, and Ghosh P 2007 Organometallics 26 958; (c) Ray L, Shaikh M M, Ghosh P 2007 Dalton Trans. 4546

  9. Dash C, Shaikh M M and Ghosh P 2009 Eur. J. Inorg. Chem. 1608

  10. (a) John A, Shaikh M M and Ghosh P 2009 Dalton Trans. 10581; (b) Samantaray M K; Shaikh M M and Ghosh P 2009 J. Organomet. Chem. 694 3477; (b) Ray L, Barman S, Shaikh M M and Ghosh P 2008 Chem. Eur. J. 14 6646

  11. (a) Samantaray M K, Shaikh M M and Ghosh P 2009 Organometallics 28 2267; (b) Ray S, Shaikh M M and Ghosh P 2009 Eur. J. Inorg. Chem. 1932

  12. (a) Ray L, Katiyar V, Barman S; Raihan M J, Nanavati H, Shaikh M M and Ghosh P 2007 J. Organomet. Chem. 692 4259; (b) Samantaray M K, Katiyar V, Pang K, Nanavati H and Ghosh P 2007 J. Organomet. Chem. 692 1672; (c) Ray L, Katiyar V, Raihan M J, Nanavati H, Shaikh M M and Ghosh P 2006 Eur. J. Inorg. Chem. 3724; (d) Samantaray M K, Katiyar V, Roy D, Pang K, Nanavati H, Stephen R, Sunoj R B and Ghosh P 2006 Eur. J. Inorg. Chem. 2975

  13. Dallacker F and Minn K 1986 Chemiker-Zeitung 110 101

    CAS  Google Scholar 

  14. Bulger P G, Cottrell I F, Cowden C J, Davies A J and Dolling U-H 2000 Tetrahedron Lett. 41 1297

    Article  CAS  Google Scholar 

  15. Brandys M-C, Jennings M C and Puddephatt R J 2000 J. Chem. Soc., Dalton Trans. 4601

  16. Kiyotsuka Y, Acharya H P, Katayama Y, Hyodo T and Kobayashi Y 2008 Org. Lett. 10 1719

    Article  CAS  Google Scholar 

  17. (a) Sheldrick G M 1997 SHELXL-97, Program for refinement of crystal structures (Germany: University of Gottingen); (b) Sheldrick G M 1997 SHELXS-97, Structure solving program (Germany: University of Gottingen)

  18. Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A Jr, Vreven T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin R L, Fox D J, Keith T, Al-Laham M A, Peng C Y, Nanayakkara A, Challacombe M, Gill P M W, Johnson B, Chen W, Wong M W, Gonzalez C and Pople J A 2004 GAUSSIAN 03: Gaussian 03, Revision C.02, Gaussian, Inc., (Wallingford, CT)

    Google Scholar 

  19. Becke A D 1988 Phys. Rev. A 38 3098

    Article  CAS  Google Scholar 

  20. (a) Alkauskas A, Baratoff A and Bruder C 2004 J. Phys. Chem. A 108 6863; (b) Andrae D, Häussermann U, Dolg M, Stoll H and Preuß H 1990 Theor. Chim. Acta 77 123

  21. Hehre W J, Ditchfield R and Pople J A 1972 J. Chem. Phys. 56 2257

    Article  CAS  Google Scholar 

  22. Reed A E, Curtiss L A and Wienhold F 1988 Chem. Rev. 88 899

    Article  CAS  Google Scholar 

  23. Dapprich S and Frenking G 1995 J. Phys. Chem. 99 9352

    Article  CAS  Google Scholar 

  24. (a) Vyboishchikov S F and Frenking G 1998 Chem. Eur. J. 8 4 1439; (b) Frenking G and Pidun U 1997 J. Chem. Soc., Dalton Trans. 1653

  25. Gorelsky S I 1997 AOMix: Program for molecular orbital analysis. (Toronto, Canada: York University); http://www.sg-chem.net/ (accessed June 27, 2009)

    Google Scholar 

  26. Gorelsky S I, Ghosh S and Solomon E I 2006 J. Am. Chem. Soc. 128 278

    Article  CAS  Google Scholar 

  27. Pauling L 1960 The nature of the chemical bond (Ithaca, NY: Cornell University Press) 3rd edn, p 224–228, 256–258

    Google Scholar 

  28. Bondi A 1964 J. Phys. Chem. 68 441

    Article  CAS  Google Scholar 

  29. Guerret O, Solé S, Gornitzka H, Teichert M, Trinquier G and Bertrand G 1997 J. Am. Chem. Soc. 119 6668

    Article  CAS  Google Scholar 

  30. Guerret O, Solé S, Gornitzka H, Trinquier G and Bertrand G 2000 J. Organomet. Chem. 600 112

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India

    CHANDRAKANTA DASH & PRASENJIT GHOSH

  2. National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India

    MOBIN M SHAIKH

Authors
  1. CHANDRAKANTA DASH
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. MOBIN M SHAIKH
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. PRASENJIT GHOSH
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to PRASENJIT GHOSH.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

(DOC 1.59 MB)

Rights and permissions

Reprints and permissions

About this article

Cite this article

DASH, C., SHAIKH, M.M. & GHOSH, P. Silver complexes of 1,2,4-triazole derived N-heterocyclic carbenes: Synthesis, structure and reactivity studies. J Chem Sci 123, 97–106 (2011). https://doi.org/10.1007/s12039-011-0105-4

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-011-0105-4

Keywords

Search

Navigation