Skip to main content
SpringerLink
Log in

Frustrated Lewis pairs: Design and reactivity

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

Abstract

The interaction of a Lewis acid with a Lewis base results in the formation of a Lewis acid–base adduct. Understanding Lewis acids and bases is central to conceptualizing chemical interactions and constitutes a major portion of metal–ligand chemistry. Sterically encumbered/constrained Lewis pairs cannot form acid–base adducts, but such ‘Frustrated Lewis Pairs’ (FLPs), with their unquenched electronic demands can be elegantly used to simultaneously react with a third species, resulting in unusual reactivity of small molecules. Such unusual reactions, explored only in the last few years, have found several applications, e.g., heterolytic splitting of H2, activation of small molecules (CO2, N2O, etc.). FLPs have opened new opportunities in synthetic chemistry, covering organic, main group as well as transition metal chemistry. The design strategies adopted for FLP systems and their unique reactivity are discussed here.

The chemistry of Frustrated Lewis acid–base pairs (FLPs) has come up with new opportunities in catalysis and covalent bond-activation in recent times. A brief overview on the design principles and the reactivity of such FLPs are presented in this review article.

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

Scheme 1
Scheme 2
Scheme 3
Figure 1
Figure 2
Figure 3
Figure 4
Scheme 4
Scheme 5
Scheme 6
Scheme 7
Figure 5
Scheme 8
Scheme 9
Figure 6
Scheme 10
Scheme 11
Figure 7
Scheme 12
Scheme 13
Scheme 14
Figure 8
Scheme 15
Scheme 16
Figure 9
Scheme 17
Figure 10
Scheme 18
Scheme 19
Figure 11
Scheme 20
Figure 12
Figure 13
Scheme 21
Scheme 22

Similar content being viewed by others

References

  1. Brønsted, J N 1923 Recl. Trav. Chim. Pays-Bas. 42, 718.

  2. Lewis G N 1923 Valence and the structure of atoms and molecules (New York: Chemical Catalogue Company)

  3. Lowry T M 1923 J. Soc. Chem. Ind. 42 43

  4. (a) Brown H C, Schlesinger H I and Cardon S Z 1942 J. Am. Chem. Soc. 64 325; (b) Brown H C and Kanner B 1966 J. Am. Chem. Soc. 88 986

  5. Wittig G and Benz E 1959 Chem. Ber. 92 1999

  6. Roesler R, Piers W E and Parvez M 2003 J. Organomet. Chem. 680 218

  7. Tochtermann W 1966 Angew. Chem. Int. Ed. Engl. 5 351

  8. Welch G C, Juan R R S, Masuda J D and Stephan D W 2006 Science 314 1124

  9. (a) Rokob T A, Hamza A, Stirling A, Soós T and Pápai I 2008 Angew. Chem. Int. Ed. 47 2435; (b) Hamza A, Stirling A, Rokob T A and Pápai I 2009 Int. J. Quantum Chem. 109 2416; (c) Bakó I, Stirling A, Bálinta S and Pápai I 2012 Dalton Trans. 41 9023

  10. (a) Grimme S, Kruse H, Goerigk L and Erker G 2010 Angew. Chem., Int. Ed. 49 1402; (b) Schirmer B and Grimme S 2010 Chem. Commun. 46 7942; (c) Rokob T A, Bako I, Stirling A, Hamza A and Papai I J. Am. Chem. Soc. 135 4425

  11. Welch G C and Stephan D W 2007 J. Am. Chem. Soc. 129 1880

  12. (a) Spies P, Erker G, Kehr G, Bergander K, Frohlich R, Grimme S and Stephan D W 2007 Chem. Commun. 5072–5074; (b) Spies P, Schwendemann S, Lange S, Kehr G, Fröhlich R and Erker G 2008 Angew. Chem. Int. Ed. 47 7543; (c) Bertini F, Lyaskovskyy V, Timmer B J J, de Kanter F J J, Lutz M, Ehlers A W, Slootweg J C, Lammertsma Koop 2012 J. Am. Chem. Soc. 134 201

  13. (a) Jackson R D, James S, Orpen A G and Pringle P G 1993 J. Organomet. Chem. 458 C3-C4; (b) Wang H, Fröhlich R, Kehr G and Erker G 2008 Chem. Commun. 5966

  14. Ullrich M, Lough A J and Stephan D W 2009 J. Am. Chem. Soc. 131 52

  15. Geier S, Gilbert T M and Stephan D W 2008 J. Am. Chem. Soc. 130 12632

  16. (a) Chen D and Klankermayer J 2008 Chem. Commun. 2130; (b) Chen D, Wang Y and Klankermayer J 2010 Angew. Chem. Int. Ed. 49 9475

  17. (a) Sajid M, Kehr G, Wiegand T, Eckert H, Schwickert C, Pöttgen R, Cardenas A J P, Warren T H, Fröhlich R, Daniliuc C G and Erker G 2013 J. Am. Chem. Soc. 135 8882; (b) Sudhakar P and Thilagar P 2013 J. Chem. Sci. 125 41

  18. (a) Chase P A, Jurca T and Stephan D W 2008 Chem. Commun. 1701; (b) Sumerin V, Schulz F, Nieger M, Leskela M, Repo T and Rieger B 2008 Angew. Chem. Int. Ed. 47 6001; (c) Sumerin V, Schulz F, Atsumi M, Wang C, Nieger M, Leskela M, Repo T, Pyykko P and Rieger B 2008 J. Am. Chem. Soc. 130 14117

  19. Geier S J and Stephan D W 2009 J. Am. Chem. Soc. 131 3476

  20. Theuergarten E, Schlüns D, Grunenberg J, Daniliuc C G, Jones P G and Tamm M 2010 Chem. Commun. 46 8561

  21. Herrington T J, Thom A J W, White A J P and Ashley A E 2012 Dalton Trans. 41 9019

  22. Caputo C B, Zhu K, Vukotic V N, Loeb S J and Stephan D W 2013 Angew. Chem. Int. Ed. 52 960

  23. Frey G D, Lavallo V, Donnadieu B, Schoeller W W and Bertrand G 2007 Science 316 439

  24. (a) Chase P A, Stephan D W 2008 Angew. Chem. Int. Ed. 47 7433; (b) Holschumacher D, Bannenberg T, Hrib C G, Jones P G and Tamm M 2008 Angew. Chem. Int. Ed. 47 7428

  25. Ménard G and Stephan D W 2010 J. Am. Chem. Soc. 132 1796

  26. (a) Ménard G and Stephan D W 2011 Angew. Chem. Int. Ed. 50 8396; (b) Ménard G and Stephan D W 2012 Angew. Chem. Int. Ed. 51 8272

  27. Ménard G, Hatnean J A, Cowley H J, Lough A J, Rawson J M and Stephan D W 2013 J. Am. Chem. Soc. 135 6446

  28. Holtrichter-Rößmann T, Isermann J, Rösener C, Cramer B, Daniliuc C-G, Kösters J, Letzel M, Würthwein E-U and Uhl W 2013 Angew. Chem. Int. Ed. 52 7135

  29. Chapman A M, Haddow M F and Wass D F 2011 J. Am. Chem. Soc. 133 8826

  30. Chapman A M, Haddow M F and Wass D F 2011 J. Am. Chem. Soc. 133 18463

  31. Xu X, Kehr G, Daniliuc C G and Erker G 2013 J. Am. Chem. Soc. 135 6465

  32. Jiang Y, Blacque O, Fox T and Berke H 2013 J. Am. Chem. Soc. 135 7751

  33. Tutusaus O, Ni C and Szymczak N K 2013 J. Am. Chem. Soc. 135 3403

  34. Sgro M J and Stephan D W 2012 Angew. Chem. Int. Ed. 51 11343

Download references

Author information

Authors and Affiliations

  1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560 012, India

    SANJOY MUKHERJEE & PAKKIRISAMY THILAGAR

Authors
  1. SANJOY MUKHERJEE
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. PAKKIRISAMY THILAGAR
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to PAKKIRISAMY THILAGAR.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

MUKHERJEE, S., THILAGAR, P. Frustrated Lewis pairs: Design and reactivity. J Chem Sci 127, 241–255 (2015). https://doi.org/10.1007/s12039-015-0783-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-015-0783-4

Keywords

Search

Navigation