Transition Metal Chemistry

, Volume 38, Issue 1, pp 113–118 | Cite as

A general method for the preparation of N-heterocyclic carbene–silver(I) complexes in water



A new synthetic method leading to N-heterocyclic carbene–silver(I) complexes [(R2-NHC)2Ag]+ [AgX2] is developed by using benzimidazolium compounds, NaOH (as a base), silver salts and water (as the reaction medium). Single-crystal X-ray structure revealed that compound 1 comprises a linear [Ag-(Et2-Bimy)2]+ cation and a linear [AgBr2] anion. These two ions are linked through an AgI–AgI association and staggered at an angle of 90.3°.


  1. 1.
    Arduengo AJ, Harlow RL, Kline M (1991) A stable crystalline carbene. J Am Chem Soc 113(1):361–363. doi:10.1021/ja00001a054 CrossRefGoogle Scholar
  2. 2.
    Huang J, Grasa G, Nolan SP (1999) General and efficient catalytic amination of aryl chlorides using a palladium/bulky nucleophilic carbene system. Org Lett 1(8):1307–1309. doi:10.1021/ol990987d CrossRefGoogle Scholar
  3. 3.
    Nair V, Bindu S, Sreekumar V (2004) N-heterocyclic carbenes: reagents, not just ligands! Angew Chem Int Ed 43(39):5130–5135. doi:10.1002/anie.200301714 CrossRefGoogle Scholar
  4. 4.
    Nolan SP (2006) N-heterocyclic carbenes in synthesis. Wiley, WeinheimCrossRefGoogle Scholar
  5. 5.
    Bourissou D, Guerret O, Gabbai FP, Bertrand G (2000) Stable carbenes. Chem Rev 100(1):39–92CrossRefGoogle Scholar
  6. 6.
    Berthon-Gelloz G, Markó IE (2006) Efficient and selective hydrosilylation of alkenes and alkynes catalyzed by novel N-heterocyclic carbene Pt0 complexes. In: N-heterocyclic carbenes in synthesis. Wiley, New York, pp 119–161. doi:10.1002/9783527609451.ch6
  7. 7.
    Gade LH, César V, Bellemin-Laponnaz S (2004) A modular assembly of chiral oxazolinylcarbene–rhodium complexes: efficient phosphane-free catalysts for the asymmetric hydrosilylation of dialkyl ketones. Angew Chem Int Ed 43(8):1014–1017. doi:10.1002/anie.200353133 CrossRefGoogle Scholar
  8. 8.
    Bantreil X, Nolan SP (2011) Synthesis of N-heterocyclic carbene ligands and derived ruthenium olefin metathesis catalysts. Nat Protoc 6(1):69–77CrossRefGoogle Scholar
  9. 9.
    Chen AC, Ren L, Decken A, Crudden CM (2000) Rhodium carbene complexes: highly selective catalysts for the hydroformylation of styrene derivatives. Organometallics 19(18):3459–3461. doi:10.1021/om0003739 CrossRefGoogle Scholar
  10. 10.
    Okuyama K-i, Sugiyama J-i, Nagahata R, Asai M, Ueda M, Takeuchi K (2003) Direct synthesis of polycarbonate from carbon monoxide and bisphenol a catalyzed by Pd–carbene complex. Macromolecules 36(19):6953–6955. doi:10.1021/ma034442h CrossRefGoogle Scholar
  11. 11.
    Vehlow K, Wang D, Buchmeiser MR, Blechert S (2008) Alternating copolymerizations using a Grubbs-type initiator with an unsymmetrical, chiral N-heterocyclic carbene ligand. Angew Chem Int Ed 47(14):2615–2618. doi:10.1002/anie.200704822 CrossRefGoogle Scholar
  12. 12.
    Lee S, Hartwig JF (2001) Improved catalysts for the palladium-catalyzed synthesis of oxindoles by amide Π± -arylation. Rate acceleration, use of aryl chloride substrates, and a new carbene ligand for asymmetric transformations. J Org Chem 66(10):3402–3415. doi:10.1021/jo005761z CrossRefGoogle Scholar
  13. 13.
    Özdemir I, Demir S, Çetinkaya B, Gourlaouen C, Maseras F, Bruneau C, Dixneuf PH (2008) Direct arylation of arene C−H bonds by cooperative action of NHCarbene−ruthenium(II) catalyst and carbonate via proton abstraction mechanism. J Am Chem Soc 130(4):1156–1157. doi:10.1021/ja710276x CrossRefGoogle Scholar
  14. 14.
    Stauffer SR, Lee S, Stambuli JP, Hauck SI, Hartwig JF (2000) High turnover number and rapid, room-temperature amination of chloroarenes using saturated carbene ligands. Org Lett 2(10):1423–1426. doi:10.1021/ol005751k CrossRefGoogle Scholar
  15. 15.
    Powell MT, Hou D-R, Perry MC, Cui X, Burgess K (2001) Chiral imidazolylidine ligands for asymmetric hydrogenation of aryl alkenes. J Am Chem Soc 123(36):8878–8879. doi:10.1021/ja016011p CrossRefGoogle Scholar
  16. 16.
    Perry MC, Cui X, Powell MT, Hou D-R, Reibenspies JH, Burgess K (2002) Optically active iridium imidazol-2-ylidene-oxazoline complexes: preparation and use in asymmetric hydrogenation of arylalkenes. J Am Chem Soc 125(1):113–123. doi:10.1021/ja028142b CrossRefGoogle Scholar
  17. 17.
    Gade LH, Bellemin-Laponnaz Sp (2007) Mixed oxazoline-carbenes as stereodirecting ligands for asymmetric catalysis. Coord Chem Rev 251(5–6):718–725CrossRefGoogle Scholar
  18. 18.
    Barnard PJ, Baker MV, Berners-Price SJ, Day DA (2004) J Inorg Biochem 98:1642CrossRefGoogle Scholar
  19. 19.
    Lin IJB, Vasam CS (2007) Preparation and application of N-heterocyclic carbene complexes of Ag(I). Coord Chem Rev 251(5–6):642–670CrossRefGoogle Scholar
  20. 20.
    Hermann WA, Koher C, GooDen LJ, Artus GRJ (1996) Chem Eur J 2:1627CrossRefGoogle Scholar
  21. 21.
    Guerret O, Solé S, Gornitzka H, Teichert M, Trinquier G, Bertrand G (1997) 1,2,4-triazole-3,5-diylidene: a building block for organometallic polymer synthesis. J Am Chem Soc 119(28):6668–6669. doi:10.1021/ja964191a CrossRefGoogle Scholar
  22. 22.
    Guerret O, Solé S, Gornitzka H, Trinquier G, Bertrand G (2000) 1,2,4-triazolium-5-ylidene and 1,2,4-triazol-3,5-diylidene as new ligands for transition metals. J Organomet Chem 600(1–2):112–117CrossRefGoogle Scholar
  23. 23.
    Citadelle CA, Nouy EL, Bisaro F, Slawin AMZ, Cazin CSJ (2010) Simple and versatile synthesis of copper and silver N-heterocyclic carbene complexes in water or organic solvents. Dalton Trans 39(19):4489–4491CrossRefGoogle Scholar
  24. 24.
    Pilarski B (1983) A new method for N-alkylation of imidazoles and benzimidazoles. Liebigs Ann Chem 6:1078–1080. doi:10.1002/jlac.198319830619 CrossRefGoogle Scholar
  25. 25.
    Singh K, Long JR, Stavropoulos P (1997) Ligand-unsupported metal−metal (M=Cu, Ag) interactions between closed-shell d10 trinuclear systems. J Am Chem Soc 119(12):2942–2943. doi:10.1021/ja963664a CrossRefGoogle Scholar
  26. 26.
    Lee KM, Wang HMJ, Lin IJB (2002) Structural diversity of N-heterocyclic carbene complexes of silver(i). J Chem Soc Dalton Trans 14:2852–2856CrossRefGoogle Scholar
  27. 27.
    Huang W, Zhang R, Zou G, Tang J, Sun J (2007) An iodide/anion exchange route to benzimidazolylidene silver complexes from benzimidazolium iodide: crystal structures of N, N’-dibutylbenzimidazolylidene silver chloride, bromide, cyanide and nitrate. J Organomet Chem 692(17):3804–3809CrossRefGoogle Scholar
  28. 28.
    Sheldrick GM (1997) SHELX-97, program for crystal structure solution. University of Goettingen, GermanyGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2012

Authors and Affiliations

  1. 1.Department of Applied ChemistryGovernment College University FaisalabadFaisalabadPakistan
  2. 2.School of ChemistryUniversity of the ManchesterManchesterUK

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