Non-conventional Lewis Acids and Bases in Frustrated Lewis Pair Chemistry

  • Christopher B. Caputo
  • Douglas W. StephanEmail author
Part of the Structure and Bonding book series (STRUCTURE, volume 171)


The discovery of frustrated Lewis pairs (FLPs) was based on the reactions of combinations of sterically demanding phosphine donors and electrophilic boranes with dihydrogen. Since these early findings, the range of species that exhibit FLP chemistry has broadened dramatically to include a series of Lewis acids and bases. In this review, we describe a variety of such systems and the corresponding reactivity of FLPs derived from group 13–16 species.


Activation of small molecules Catalysis Frustrated Lewis pairs Lewis acids Lewis bases 





Diisobutylaluminium hydride


Electron paramagnetic resonance


Frustrated Lewis pair


Frustrated radical pair










Methyl methacrylate




N-Heterocyclic carbene


Nuclear magnetic resonance














  1. 1.
    Lewis GN (1916) J Am Chem Soc 38:762–785CrossRefGoogle Scholar
  2. 2.
    Lewis GN (1923) Valence and the structure of atoms and molecules. Chemical Catalogue , New YorkGoogle Scholar
  3. 3.
    Groves JK (1972) Chem Soc Rev 1:73–97CrossRefGoogle Scholar
  4. 4.
    Rueping M, Nachtsheim BJ (2010) Beilstein J Org Chem 6:6CrossRefGoogle Scholar
  5. 5.
    Tolman CA (1977) Chem Rev 77:313–348CrossRefGoogle Scholar
  6. 6.
    Tang W, Zhang X (2003) Chem Rev 103:3029–3069CrossRefGoogle Scholar
  7. 7.
    Denmark SE, Beutner GL (2008) Angew Chem Int Ed 47:1560–1638CrossRefGoogle Scholar
  8. 8.
    Brown HC, Schlesinger HI, Cardon SZ (1942) J Am Chem Soc 64:325–329CrossRefGoogle Scholar
  9. 9.
    Wittig G, Ruckert A (1950) Ann Chem Just Lieb 566:101–113CrossRefGoogle Scholar
  10. 10.
    Wittig G, Benz E (1959) Chem Ber 92:1999–2013CrossRefGoogle Scholar
  11. 11.
    Tochtermann W (1966) Angew Chem Int Ed 5:351–371CrossRefGoogle Scholar
  12. 12.
    Doering S, Erker G, Fröhlich R, Meyer O, Bergander K (1998) Organometallics 17:2183–2187CrossRefGoogle Scholar
  13. 13.
    Welch GC, Cabrera L, Chase PA, Hollink E, Masuda JD, Wei PR, Stephan DW (2007) Dalton Trans 3407–3414Google Scholar
  14. 14.
    Cabrera L, Welch GC, Masuda JD, Wei PR, Stephan DW (2006) Inorg Chim Acta 359:3066–3071CrossRefGoogle Scholar
  15. 15.
    Welch GC, Juan RRS, Masuda JD, Stephan DW (2006) Science 314:1124–1126CrossRefGoogle Scholar
  16. 16.
    Welch GC, Stephan DW (2007) J Am Chem Soc 129:1880–1881CrossRefGoogle Scholar
  17. 17.
    Stephan DW, Erker G (2010) Angew Chem Int Ed 49:46–76CrossRefGoogle Scholar
  18. 18.
    Stephan DW, Erker G (2015) Angew Chem Int Ed 54:6400–6441CrossRefGoogle Scholar
  19. 19.
    Stephan DW, Erker G (2013) Top Curr Chem 332:85–110CrossRefGoogle Scholar
  20. 20.
    Stephan DW, Erker G (eds) (2013) Frustrated Lewis Pairs II, expanding the scope, vol 334. Springer, BerlinGoogle Scholar
  21. 21.
    Greb L, Oña-Burgos P, Schirmer B, Grimme S, Stephan DW, Paradies J (2012) Angew Chem Int Ed 51:10164–10168CrossRefGoogle Scholar
  22. 22.
    Spies P, Erker G, Kehr G, Bergander K, Fröhlich R, Grimme S, Stephan DW (2007) Chem Commun 5072–5074Google Scholar
  23. 23.
    Greb L, Tussing S, Schirmer B, Oña-Burgos P, Kaupmees K, Lõkov M, Leito I, Grimme S, Paradies J (2013) Chem Sci 4:2788–2796CrossRefGoogle Scholar
  24. 24.
    Geier SJ, Stephan DW (2009) J Am Chem Soc 131:3476–3477CrossRefGoogle Scholar
  25. 25.
    Sumerin V, Schulz F, Nieger M, Leskelä M, Repo T, Rieger B (2009) Angew Chem 121:10023–10027CrossRefGoogle Scholar
  26. 26.
    Sumerin V, Schulz F, Nieger M, Leskelä M, Repo T, Rieger B (2008) Angew Chem 47:6001–6003CrossRefGoogle Scholar
  27. 27.
    Chernichenko K, Madarász Á, Pápai I, Nieger M, Leskelä M, Repo T (2013) Nat Chem 5:718–723CrossRefGoogle Scholar
  28. 28.
    Caputo CB, Geier SJ, Winkelhaus D, Mitzel NW, Vukotic VN, Loeb SJ, Stephan DW (2012) Dalton Trans 41:2131–2139CrossRefGoogle Scholar
  29. 29.
    Farrell JM, Hatnean JA, Stephan DW (2012) J Am Chem Soc 134:15728–15731CrossRefGoogle Scholar
  30. 30.
    Chase PA, Welch GC, Jurca T, Stephan DW (2007) Angew Chem Int Ed 46:8050–8053CrossRefGoogle Scholar
  31. 31.
    Chase PA, Jurca T, Stephan DW (2008) Chem Commun 1701–1703Google Scholar
  32. 32.
    Farrell JM, Posaratnanathan RT, Stephan DW (2015) Chem Sci 6:2010–2015CrossRefGoogle Scholar
  33. 33.
    Eisenberger P, Bestvater BP, Keske EC, Crudden CM (2015) Angew Chem Int Ed 54:2467–2471CrossRefGoogle Scholar
  34. 34.
    de Oliveira Freitas LB, Eisenberger P, Crudden CM (2013) Organometallics 32:6635–6638CrossRefGoogle Scholar
  35. 35.
    Huisgen R (1961) Proc Chem Soc 357–396Google Scholar
  36. 36.
    Lawrence EJ, Oganesyan VS, Hughes DL, Ashley AE, Wildgoose GG (2014) J Am Chem Soc 136:6031–6036CrossRefGoogle Scholar
  37. 37.
    Fan C, Piers WE, Parvez M (2009) Angew Chem Int Ed 48:2955–2958CrossRefGoogle Scholar
  38. 38.
    Fan C, Mercier LG, Piers WE, Tuononen HM, Parvez M (2010) J Am Chem Soc 132:9604–9606CrossRefGoogle Scholar
  39. 39.
    Houghton AY, Hurmalainen J, Mansikkamäki A, Piers WE, Tuononen HM (2014) Nat Chem 983–988Google Scholar
  40. 40.
    Zheng J, Wang Y, Li ZH, Wang H (2015) Chem Commun 51:5505–5508CrossRefGoogle Scholar
  41. 41.
    Dureen MA, Stephan DW (2009) J Am Chem Soc 131:8396–8397CrossRefGoogle Scholar
  42. 42.
    Dureen MA, Brown CC, Stephan DW (2010) Organometallics 29:6594–6607CrossRefGoogle Scholar
  43. 43.
    Ménard G, Stephan DW (2012) Angew Chem Int Ed 51:8272–8275CrossRefGoogle Scholar
  44. 44.
    Hatnean JA, Thomson JW, Chase PA, Stephan DW (2014) Chem Commun 50:301–303CrossRefGoogle Scholar
  45. 45.
    Ménard G, Stephan DW (2010) J Am Chem Soc 132:1796–1797CrossRefGoogle Scholar
  46. 46.
    Ménard G, Stephan DW (2011) Angew Chem Int Ed 50:8396–8399CrossRefGoogle Scholar
  47. 47.
    Ménard G, Gilbert TM, Hatnean JA, Kraft A, Krossing I, Stephan DW (2013) Organometallics 32:4416–4422CrossRefGoogle Scholar
  48. 48.
    Otten E, Neu RC, Stephan DW (2009) J Am Chem Soc 131:9918–9919CrossRefGoogle Scholar
  49. 49.
    Ménard G, Hatnean JA, Cowley HJ, Lough AJ, Rawson JM, Stephan DW (2013) J Am Chem Soc 135:6446–6449CrossRefGoogle Scholar
  50. 50.
    Sajid M, Stute A, Cardenas AJP, Culotta BJ, Hepperle JAM, Warren TH, Schirmer B, Grimme S, Studer A, Daniliuc CG, Fröhlich R, Petersen JL, Kehr G, Erker G (2012) J Am Chem Soc 134:10156–10168CrossRefGoogle Scholar
  51. 51.
    McCahill JSJ, Welch GC, Stephan DW (2009) Angew Chem 121:10023–10027CrossRefGoogle Scholar
  52. 52.
    McCahill JSJ, Welch GC, Stephan DW (2009) Angew Chem 46:4968–4971CrossRefGoogle Scholar
  53. 53.
    Ménard G, Stephan DW (2012) Angew Chem Int Ed 51:4409–4412CrossRefGoogle Scholar
  54. 54.
    Ménard G, Tran L, McCahill JSJ, Lough AJ, Stephan DW (2013) Organometallics 32:6759–6763CrossRefGoogle Scholar
  55. 55.
    Zhang YT, Miyake GM, Chen EYX (2010) Angew Chem Int Ed 49:10158–10162CrossRefGoogle Scholar
  56. 56.
    Xu T, Chen EY (2014) J Am Chem Soc 136:1774–1777CrossRefGoogle Scholar
  57. 57.
    He JH, Zhang YT, Chen EYX (2014) Synlett 25:1534–1538CrossRefGoogle Scholar
  58. 58.
    Chen EX (2013) In: Erker G, Stephan DW (eds) Frustrated Lewis Pairs II, vol 334. Springer, Berlin, p 239CrossRefGoogle Scholar
  59. 59.
    Appelt C, Westenberg H, Bertini F, Ehlers AW, Slootweg JC, Lammertsma K, Uhl W (2011) Angew Chem Int Ed 50:3925–3928CrossRefGoogle Scholar
  60. 60.
    Mömming CM, Otten E, Kehr G, Fröhlich R, Grimme S, Stephan DW, Erker G (2009) Angew Chem Int Ed 48:6643–6646CrossRefGoogle Scholar
  61. 61.
    Appelt C, Slootweg JC, Lammertsma K, Uhl W (2013) Angew Chem Int Ed 52:4256–4259CrossRefGoogle Scholar
  62. 62.
    Roters S, Appelt C, Westenberg H, Hepp A, Slootweg J, Lammertsma K, Uhl W (2012) Dalton Trans 41:9033–9045CrossRefGoogle Scholar
  63. 63.
    Holtrichter-Rossmann T, Isermann J, Rosener C, Cramer B, Daniliuc CG, Kosters J, Letzel M, Wurthwein EU, Uhl W (2013) Angew Chem Int Ed 52:7135–7138CrossRefGoogle Scholar
  64. 64.
    Holtrichter-Rossmann T, Rosener C, Hellmann J, Uhl W, Wurthwein EU, Frohlich R, Wibbeling B (2012) Organometallics 31:3272–3283CrossRefGoogle Scholar
  65. 65.
    Bourissou D, Guerret O, Gabbaï FP, Bertrand G (2000) Chem Rev 100:39–92CrossRefGoogle Scholar
  66. 66.
    Hopkinson MN, Richter C, Schedler M, Glorius F (2014) Nature 510:485–496CrossRefGoogle Scholar
  67. 67.
    Frey GD, Lavallo V, Donnadieu B, Schoeller WW, Bertrand G (2007) Science 316:439–441CrossRefGoogle Scholar
  68. 68.
    Chase PA, Stephan DW (2008) Angew Chem Int Ed 47:7433–7437CrossRefGoogle Scholar
  69. 69.
    Holschumacher D, Bannenberg T, Hrib CG, Jones PG, Tamm M (2008) Angew Chem Int Ed 47:7428–7432CrossRefGoogle Scholar
  70. 70.
    Kolychev EL, Bannenberg T, Freytag M, Daniliuc CG, Jones PG, Tamm M (2012) Chem Eur J 18:16938–16946CrossRefGoogle Scholar
  71. 71.
    Alcarazo M, Gomez C, Holle S, Goddard R (2010) Angew Chem Int Ed 49:5788–5791CrossRefGoogle Scholar
  72. 72.
    Boone MP, Stephan DW (2011) Organometallics 30:5537–5542CrossRefGoogle Scholar
  73. 73.
    Boone MP, Stephan DW (2014) Organometallics 33:387–393CrossRefGoogle Scholar
  74. 74.
    Neu RC, Otten E, Lough A, Stephan DW (2011) Chem Sci 2:170–176CrossRefGoogle Scholar
  75. 75.
    Runyon JW, Steinhof O, Dias HVR, Calabrese JC, Marshall WJ, Arduengo AJ (2011) Aust J Chem 64:1165–1172CrossRefGoogle Scholar
  76. 76.
    Inés B, Holle S, Goddard R, Alcarazo M (2010) Angew Chem Int Ed 49:8389–8391CrossRefGoogle Scholar
  77. 77.
    Childs RF, Mulholland DL, Nixon A (1982) Can J Chem 60:801–808CrossRefGoogle Scholar
  78. 78.
    Palomas D, Holle S, Ines B, Bruns H, Goddard R, Alcarazo M (2012) Dalton Trans 41:9073–9082CrossRefGoogle Scholar
  79. 79.
    Boone MP, Stephan DW (2013) J Am Chem Soc 135:8508–8511CrossRefGoogle Scholar
  80. 80.
    Boone MP, Stephan DW (2014) Chem Eur J 20:3333–3341CrossRefGoogle Scholar
  81. 81.
    Clark ER, Ingleson MJ (2013) Organometallics 32:6712–6717CrossRefGoogle Scholar
  82. 82.
    Clark ER, Ingleson MJ (2014) Angew Chem Int Ed 53:11306–11309CrossRefGoogle Scholar
  83. 83.
    Lambert JB, Zhang S, Ciro SM (1994) Organometallics 13:2430–2443CrossRefGoogle Scholar
  84. 84.
    Lambert JB, Zhang S, Stern CL, Huffman JC (1993) Science 260:1917–1918CrossRefGoogle Scholar
  85. 85.
    Reed CA, Xie Z, Bau R, Benesi A (1993) Science 262:402–404CrossRefGoogle Scholar
  86. 86.
    Gusev DG, Ozerov OV (2011) Chem Eur J 17:634–640CrossRefGoogle Scholar
  87. 87.
    Nava M, Reed CA (2011) Organometallics 30:4798–4800CrossRefGoogle Scholar
  88. 88.
    Schafer A, Reissmann M, Schafer A, Saak W, Haase D, Muller T (2011) Angew Chem Int Ed 50:12636–12638CrossRefGoogle Scholar
  89. 89.
    Reißmann M, Schäfer A, Jung S, Müller T (2013) Organometallics 32:6736–6744CrossRefGoogle Scholar
  90. 90.
    Schafer A, Reissmann M, Schafer A, Schmidtmann M, Muller T (2014) Chem Eur J 20:9381–9386CrossRefGoogle Scholar
  91. 91.
    Herrington TJ, Ward BJ, Doyle LR, McDermott J, White AJP, Hunt PA, Ashley AE (2014) Chem Commun 50:12753–12756CrossRefGoogle Scholar
  92. 92.
    Li J, Li Y, Purushothaman I, De S, Li B, Zhu H, Parameswaran P, Ye Q, Liu W (2015) Organometallics 150420110250005Google Scholar
  93. 93.
    Burford N, Ragogna PJ (2002) Dalton Trans 4307–4315Google Scholar
  94. 94.
    Longobardi LE, Russell CA, Green M, Townsend NS, Wang K, Holmes AJ, Duckett SB, McGrady JE, Stephan DW (2014) J Am Chem Soc 136:13453–13457CrossRefGoogle Scholar
  95. 95.
    Terada M, Kouchi M (2006) Tetrahedron 62:401–409CrossRefGoogle Scholar
  96. 96.
    Werner T (2009) Adv Synth Catal 351:1469–1481CrossRefGoogle Scholar
  97. 97.
    Hounjet LJ, Caputo CB, Stephan DW (2012) Angew Chem Int Ed 51:4714–4717CrossRefGoogle Scholar
  98. 98.
    Zhu J, An K (2013) Chem Asian J 8:3147CrossRefGoogle Scholar
  99. 99.
    Cavell RG, The KI, Griend LV (1981) Inorg Chem 20:3813–3818CrossRefGoogle Scholar
  100. 100.
    Cavell RG, Vandegriend L (1983) Inorg Chem 22:2066–2070CrossRefGoogle Scholar
  101. 101.
    Cavell RG, Vandegriend L (1986) Inorg Chem 25:4699–4704CrossRefGoogle Scholar
  102. 102.
    Hounjet LJ, Caputo CB, Stephan DW (2013) Dalton Trans 42:2629–2635CrossRefGoogle Scholar
  103. 103.
    Ullrich M, Lough AJ, Stephan DW (2009) J Am Chem Soc 131:52–53CrossRefGoogle Scholar
  104. 104.
    Caputo CB, Winkelhaus D, Dobrovetsky R, Hounjet LJ, Stephan DW (2015) Dalton Trans 44. doi:10.1039/C1035DT00217FGoogle Scholar
  105. 105.
    Caputo CB, Hounjet LJ, Dobrovetsky R, Stephan DW (2013) Science 341:1374–1377CrossRefGoogle Scholar
  106. 106.
    Perez M, Hounjet LJ, Caputo CB, Dobrovetsky R, Stephan DW (2013) J Am Chem Soc 135:18308–18310CrossRefGoogle Scholar
  107. 107.
    Perez M, Qu ZW, Caputo CB, Podgorny V, Hounjet LJ, Hansen A, Dobrovetsky R, Grimme S, Stephan DW (2015) Chem Eur J 21:6491–6500CrossRefGoogle Scholar
  108. 108.
    Perez M, Caputo CB, Dobrovetsky R, Stephan DW (2014) Proc Natl Acad Sci U S A 111:10917–10921CrossRefGoogle Scholar
  109. 109.
    Parks DJ, Blackwell JM, Piers WE (2000) J Org Chem 65:3090–3098CrossRefGoogle Scholar
  110. 110.
    Rendler S, Oestreich M (2008) Angew Chem Int Ed 47:5997–6000CrossRefGoogle Scholar
  111. 111.
    Holthausen MH, Mehta M, Stephan DW (2014) Angew Chem Int Ed 53:6538–6541CrossRefGoogle Scholar
  112. 112.
    Jiang C, Blacque O, Berke H (2009) Chem Commun 5518–5520Google Scholar
  113. 113.
    Piers WE, Irvine GJ, Williams VC (2000) Eur J Inorg Chem 2131–2142Google Scholar
  114. 114.
    Holthausen MH, Hiranandani RR, Stephan DW (2015) Chem Sci 6:2016–2021CrossRefGoogle Scholar
  115. 115.
    Caputo CB, Zhu KL, Vukotic VN, Loeb SJ, Stephan DW (2013) Angew Chem Int Ed 52:960–963CrossRefGoogle Scholar
  116. 116.
    Dobrovetsky R, Stephan DW (2013) J Am Chem Soc 135:4974–4977CrossRefGoogle Scholar
  117. 117.
    Hounjet LJ, Bannwarth C, Garon CN, Caputo CB, Grimme S, Stephan DW (2013) Angew Chem Int Ed 52:7492–7495CrossRefGoogle Scholar
  118. 118.
    Longobardi LE, Tang C, Stephan DW (2014) Dalton Trans 43:15723–15726CrossRefGoogle Scholar
  119. 119.
    Lindqvist M, Sarnela N, Sumerin V, Chernichenko K, Leskelä M, Repo T (2012) Dalton Trans 41:4310–4312CrossRefGoogle Scholar
  120. 120.
    Mahdi T, Stephan DW (2014) J Am Chem Soc 136:15809–15812CrossRefGoogle Scholar
  121. 121.
    Scott DJ, Fuchter MJ, Ashley AE (2014) J Am Chem Soc 136:15813–15816CrossRefGoogle Scholar
  122. 122.
    Jutzi P, Müller C, Stammler A, Stammler HG (2000) Organometallics 19:1442–1444CrossRefGoogle Scholar
  123. 123.
    Tanur CA, Stephan DW (2011) Organometallics 30:3652–3657CrossRefGoogle Scholar
  124. 124.
    Tsao FA, Lough AJ, Stephan DW (2015) Chem Commun 51:4287–4289CrossRefGoogle Scholar
  125. 125.
    Tsao FA, Stephan DW (2015) Dalton Trans 44:71–74CrossRefGoogle Scholar

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© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of TorontoTorontoCanada

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