Journal of Chemical Sciences

, Volume 128, Issue 11, pp 1725–1735 | Cite as

Ruthenium(II) complexes bearing pyridine-functionalized N-heterocyclic carbene ligands: Synthesis, structure and catalytic application over amide synthesis

  • MUTHUKUMARAN NIRMALA
  • PERIASAMY VISWANATHAMURTHI
Article
First Online:
Received:
Revised:
Accepted:
  • 557 Downloads

Abstract

A series of four imidazolium salts was synthesized by the reaction of 2-bromopyridine with 1-substituted imidazoles. These imidazolium salts (1a–d) were successfully employed as ligand precursors for the syntheses of new ruthenium(II) complexes bearing neutral bidentate ligands of N-heterocyclic carbene and pyridine donor moiety. The NHC-ruthenium(II) complexes (3a–d) were synthesized by reacting the appropriately substituted pyridine-functionalized N-heterocyclic carbenes with Ag2O forming the NHC–silver bromide in situ followed by transmetalation with [RuHCl(CO)(PPh3)3]. The new complexes were characterized by elemental analyses and spectroscopy (IR, UV-Vis,1H,13C,31P-NMR) as well as ESI mass spectrometry. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The complexes were shown to be efficient catalysts for the one-pot conversion of various aldehydes to their corresponding primary amides with good to excellent isolated yields using NH2OH.HCl and NaHCO3. The effects of solvent, base, temperature, time and catalyst loading were also investigated. A broad range of amides were successfully synthesized with excellent isolated yields using the above optimized protocol. Notably, the complex 3a was found to be a very efficient and versatile catalyst towards amidation of a wide range of aldehydes.

Open image in new window
Graphical Abstract

A series of ruthenium(II) complexes (3a-d) bearing pyridine functionalized N-heterocyclic carbene ligand was synthesized and characterized by FT-IR, NMR and ESI-Mass. The catalytic study of complexes (3a-d) towards one-pot conversion of various aldehydes to their corresponding primary amides was studied. This new protocol is effective broad range of amides were successfully synthesized in good to excellent yields.

Keywords

Pyridine-functionalized carbene ligand [Ru–NHC] complexes transmetalation aldehyde to amide conversion 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgements

The authors express their sincere thanks to Department of Science and Technology, New Delhi, for financial support for this work under the DST-FAST TRACK Scheme (No. SR/FT/CS-66/2011). One of the authors (MN) thanks DST-SERB for the award of fellowship.

Supplementary material

12039_2016_1169_MOESM1_ESM.docx (988 kb)
(DOCX 988 KB)

References

  1. 1.
    Lin J C Y, Huang R T W, Lee C S, Bhattacharyya A, Hwang W S and Lin I J B 2009 Chem. Rev. 109 3561CrossRefGoogle Scholar
  2. 2.
    Crabtree R H 2005 J. Organomet. Chem. 690 5451CrossRefGoogle Scholar
  3. 3.
    Dragutan V, Dragutan I, Delaude L and Demonceau A 2007 Coord. Chem. Rev. 251 765CrossRefGoogle Scholar
  4. 4.
    (a) Díez-González S, Marion N and Nolan S P 2009 Chem. Rev. 109 3612; (b) Nirmala M and Viswanathamurthi P 2016 J. Chem. Sci. 128 9; (c) Roymahapatra G, Samanta T, Seth S K, Mahapatra A, Chattopadhyay S K and Dinda J 2015 J. Chem. Sci. 127 1057; (d) Gangwar M K, Kalita A C and Ghosh P 2014 J. Chem. Sci. 126 1557Google Scholar
  5. 5.
    Hahn F E and Jahnke M C 2008 Angew. Chem., Int. Ed. 47 3122CrossRefGoogle Scholar
  6. 6.
    Herndon J W 2010 Coord. Chem. Rev. 254 103CrossRefGoogle Scholar
  7. 7.
    Nolan S P 2010 Acc. Chem. Res. 144 91Google Scholar
  8. 8.
    Velazquez H D and Verpoort F 2012 Chem. Soc. Rev. 41 7032CrossRefGoogle Scholar
  9. 9.
    Würtz S and Glorius F 2008 Acc. Chem. Res. 41 1523CrossRefGoogle Scholar
  10. 10.
    Herrmann W A 2002 Angew. Chem., Int. Ed. 41 1290CrossRefGoogle Scholar
  11. 11.
    (a) Arnold P L and Pearson S 2007 Coord. Chem. Rev. 251 596; (b) Arslan H, Özdemır I, Vanderveer D, Demır S and Çetınkaya B 2009 J. Coord. Chem. 62 2591; (c) Özdemir I, Yiğit M, Yiğit B, Çetinkaya B and Çetinkaya E 2007 J. Coord. Chem. 60 2377Google Scholar
  12. 12.
    Bouffard J, Keitz B K, Tonner R, Guisado-Barrios G, Frenking G, Grubbs R H and Bertrand G 2011 Organometallics 30 2617CrossRefGoogle Scholar
  13. 13.
    Chianese A R, Kovacevic A, Zeglis B M, Faller J W and Crabtree R H 2004 Organometallics 23 2461CrossRefGoogle Scholar
  14. 14.
    Guisado-Barrios G, Bouffard J, Donnadieu B and Bertrand G 2010 Angew. Chem., Int. Ed. 49 4759CrossRefGoogle Scholar
  15. 15.
    Han Y and Huynh H V 2007 Chem. Commun. 1089Google Scholar
  16. 16.
    Han Y, Lee L J and Huynh H V 2009 Organometallics 28 2778CrossRefGoogle Scholar
  17. 17.
    Han Y and Huynh H V 2011 Dalton Trans. 40 2141CrossRefGoogle Scholar
  18. 18.
    Lavallo V, Canac Y, Präsang C, Donnadieu B and Bertrand G 2005 Angew. Chem. Int. Ed. 44 5705CrossRefGoogle Scholar
  19. 19.
    Mathew P, Neels A and Albrecht M 2008 J. Am. Chem. Soc. 130 13534CrossRefGoogle Scholar
  20. 20.
    Melaimi M, Soleilhavoup M and Bertrand G 2010 Angew. Chem., Int. Ed. 49 8810CrossRefGoogle Scholar
  21. 21.
    (a) Ung G and Bertrand G 2011 Chem. -Eur. J. 17 8269; (b) Martin D, Melaimi M, Soleilhavoup M and Bertrand G 2011 Organometallics 30 5304Google Scholar
  22. 22.
    Hopkinson M N, Richter C, Schedler M and Glorius F 2014 Nature 510 485CrossRefGoogle Scholar
  23. 23.
    (a) Kuhl O 2007 Chem. Soc. Rev. 36 592; (b) Lee H M, Lee C C and Cheng P Y 2007 Curr. Org. Chem. 11 1491; (c) Normand A T and Cavell K J 2008 Eur. J. Inorg. Chem. 278 12800; (d) Yaşar S, Çekirdek S and Özdemir I 2014 J. Coord. Chem. 67 1236; (e) Pozo C D, Iglesias M and Sanchez F 2011 Organometallics 30 2180Google Scholar
  24. 24.
    (a) Wang C Y, Liu Y H, Peng S M and Liu S T 2006 J. Organomet. Chem. 691 4012; (b) Danopoulos A A, Winston S and Hursthouse M B 2002 J. Chem. Soc., Dalton Trans. 3090; (c) Stylianides N, Danoupolos A A and Tsoureas N 2005 J. Organomet. Chem. 690 5948; (d) Wang X, Liu S, Weng L H and Jin G X, Chem. Eur. J. 13 188Google Scholar
  25. 25.
    (a) Mas-Marz E, Sana M and Peris E 2005 Inorg. Chem. 44 9961; (b) Wang C Y, Fu C F, Liu Y H, Peng S M and Liu S T 2007 Inorg. Chem. 46 5779Google Scholar
  26. 26.
    (a) Wang X, Liu S and Jin G X 2004 Organometallics 23 6002; (b) Winston S, Stylianides N, Tulloch A A D, Wright J A and Danoupolos A A 2004 J. Organomet. Chem. 23 2813Google Scholar
  27. 27.
    (a) Magill A M, McGuinness D S, Cavell K J, Britovsek G J P, Gibson V C, White A J P, Williams D J, White A J and Skelton B W 2001 J. Organomet. Chem. 617; (b) Wang X, Liu S, Weng L H and Jin G X 2006 Organometallics 25 3565Google Scholar
  28. 28.
    Tulloch A A D, Danopoulos A A, Kleinhenz S, Light M E, Hurthouse M B and Eastham G 2001 Organometallics 20 2027CrossRefGoogle Scholar
  29. 29.
    Tulloch A A D, Danopoulos A A, Winston S, Kleinhenz S and Eastham G 2000 J. Chem. Soc., Dalton Trans. 4499Google Scholar
  30. 30.
    Dugger R W, Ragan J A and Ripin D H B 2005 Org. Process Res. Dev. 9 253CrossRefGoogle Scholar
  31. 31.
    Chen H, He M, Wang Y, Zhai L, Cui Y, Li Y, Zhou H, Hong X and Deng Z 2011 Green Chem. 13 2723CrossRefGoogle Scholar
  32. 32.
    Curtius T 2006 Berichte derdeutschen chemischen Gesellschaft 35 3226CrossRefGoogle Scholar
  33. 33.
    Gunanathan C, Ben-David Y and Milstein D 2007 Science 317 790CrossRefGoogle Scholar
  34. 34.
    Shen B, Makley D M and Johnston J N 2010 Nature 465 1027CrossRefGoogle Scholar
  35. 35.
    Sheldon R A 1994 Chem. Tech. 38Google Scholar
  36. 36.
    (a) Mabermann C E 1991 In Encyclopedia of Chemical Technology Vol. 1 (New York: Wiley) p.251; (b) Lipp D 1991 In Encyclopedia of Chemical Technology vol. 1 (New York: Wiley) p.266; (c) Opsahl R 1991 In Encyclopedia of Chemical Technology Vol. 2 (New York: Wiley) p.346Google Scholar
  37. 37.
    Constable D J C, Dunn P J, Hayler J D, Humphrey G R, Leazer J L, Linderman R J, Lorenz K, Manley J, Pearlman B A, Wells A, Zaks A and Zhang T Y 2007 Green Chem. 9 411CrossRefGoogle Scholar
  38. 38.
    (a) Tfouni E, Krieger M, Mcgarvey B R and Franco D W 2003 Coord. Chem. Rev. 236 57; (b) Coe B J and Glenwright S 2000 J. Coord. Chem. Rev. 203 5; (c) Batista A A, Pereira C, Wohnrath K, Queiroz S L, Santos R H A and Gambardella M T P 1999 Polyhedron 18 2079; (d) Poelhsitz G V, Araujo M P, Oliveira L A A, Queiroz S L, Ellena J, Castellano E E, Ferreira A G and Batista A A 2002 Polyhedron 21 2221; (e) Bastista A A, Pereira C, Queiroz S L, Oliverira L A A, Santos R H A and Gambardella M T P 1997 Polyhedron 16 927; (f) Gianferrara T, Serli B, Zangrando E, Lengo E and Alessio E 2005 New J. Chem. 29 895; (g) Serli B, Zangrando E, Lengo E, Mestroni G, Yellowlees L and Alessio E 2002 Inorg. Chem. 41 4033; (h) Videla M, Jacinto J S, Baggio R, Garland M T, Singh P, Kaim W, Slep L D and Olabe J A 2006 Inorg. Chem. 45 8608; (i) Hirano T, Ueda K, Mukaida M, Nagao H and Oi T 2001 J. Chem. Soc., Dalton Trans.2341; (j) Borges S S, Davanzo C U, Castellano E E, Schpector J, Silva S C and Franco D W 1998 Inorg. Chem. 37 2670; (k) Fortney C F and Shepherd R E 2004 Inorg. Chem. Commun. 7 1065Google Scholar
  39. 39.
    (a) Lebel H and Paquet V 2004 Organometallics 23 1187; (b) Kuwata S, Kura S and Ikariya T 2007 Polyhedron 26 4659; (c) Katho A, Opre Z, Laurenczy G and Joo F 2003 J. Mol. Catal. A: Chem. 204 143; (d) Wilson S T and Osborn J A 1971 J. Am. Chem. Soc. 93 3068Google Scholar
  40. 40.
    (a) Nørdstrom L U, Vogt H and Madsen R 2008 J. Am. Chem. Soc. 130 17672; (b) Ghosh S C, Muthaiah S, Zhang Y, Xu X and Hong S H 2009 Adv. Synth. Catal. 351 2643; (c) Zhang Y, Chen C, Ghosh S C, Li Y and Hong S H 2010 Organometallics 29 1374Google Scholar
  41. 41.
    Muthaiah S, Ghosh S C, Jee J E, Chen C, Zhang J and Hong S H 2010 J. Org. Chem. 75 3002CrossRefGoogle Scholar
  42. 42.
    Field L, Barnett P, Shumaker S H and Marshall W S 1961 J. Am. Chem. Soc. 83 1983CrossRefGoogle Scholar
  43. 43.
    Sharma S K, Bishopp S D, Allen C L, Lawrence R, Bamford B J, Lapkin A A, Plucinski P, Watson R J and Williams J M J 2011 Tetrahedron Lett. 52 4252CrossRefGoogle Scholar
  44. 44.
    (a) Gnanamgari D and Crabtree R H 2009 Organometallics 28 922; (b) Hull J F, Hilton S T and Crabtree R H 2010 Inorg. Chim. Acta 363 1243; (c) Owston N A, Parker A J and Williams J M J 2007 Org. Lett. 9 3599Google Scholar
  45. 45.
    Barfoot C, Brooks G, Brown P, Dabbs S, Davies D T, Giordano I, Hennessy A, Jones G, Markwell R, Miles T, Pearson N and Smethurst C A 2010 Tetrahedron Lett. 51 2685CrossRefGoogle Scholar
  46. 46.
    (a) Owston N A, Parker A J and Williams J M J 2007 Org. Lett. 9 73; (b) Saidi O, Bamford M J, Blacker A J, Lynch J, Marsden S P, Plucinski P, Watson R J and Williams J M J 2010 Tetrahedron Lett. 51 5804Google Scholar
  47. 47.
    Park S, Choi Y, Han H, Yang S H and Chang S 2003 Chem. Commun. 1936Google Scholar
  48. 48.
    Allen C L, Burel C and Williams J M J 2010 Tetrahedron Lett. 51 2724CrossRefGoogle Scholar
  49. 49.
    (a) Gridnev A A and Mihaltseva I M 1994 Synth. Commun. 24 1547; (b) Liu J, Chen J, Zhao J, Zhao Y, Li L and Zhang H 2003 Synthesis 17 2661; (c) Sreedhar B, Shiva Kumar K B, Srinivas P, Balasubrahmanyam V and Venkanna G T 2007 J. Mol. Catal. A: Chem. 265 183Google Scholar
  50. 50.
    Ahmed N, Levison S J, Robinson S D and Uttley M F 1974 Inorg. Synth. 15 48Google Scholar
  51. 51.
    (a) Loch J A, Albrecht M, Peris E, Mata J, Faller J W and Crabtree R H 2002 Organometallics 21 700; (b) Frey G D, Schutz J, Herdtweck E and Hermann W A 2005 Organometallics 24 4416; (c) Kaufhold O, Hahn F E, Pape T and Hepp A 2008 J. Organomet. Chem. 693 3435Google Scholar
  52. 52.
    El-Shahawi M S and Shoair A F 2004 Spectrochim. Acta A 60 121CrossRefGoogle Scholar
  53. 53.
    Tyagi D, Rai R K, Dwivedi A D, Mobin S M and Singh S K 2015 Inorg. Chem. Front. 2 116CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2016

Authors and Affiliations

  • MUTHUKUMARAN NIRMALA
    • 1
  • PERIASAMY VISWANATHAMURTHI
    • 1
  1. 1.Department of ChemistryPeriyar UniversitySalemIndia

Personalised recommendations