Synthesis, Structure, and Reactivity of Carbodiphosphoranes, Carbodicarbenes, and Related Species

  • Manuel Alcarazo
Part of the Structure and Bonding book series (STRUCTURE, volume 177)


The unique electronic distribution in carbodiphosphoranes has attracted the attention of chemists early since their first isolation. These molecules can be seen as two simultaneous ylide functionalities localized at the same carbon atom; thus, their central carbon possesses two perpendicular electron pairs available for coordination. Recent theoretical studies point that the bonding situation in these compounds is best described using a captodative model; that means, in terms of donor acceptor interactions Open image in new window . Hence, carbodiphosphoranes can be seen as C(0) atoms stabilized by two flanking phosphines. Although not always free of controversy, the fact is that this analysis is extremely useful to predict and understand the reactivity of carbodiphosphoranes of different structure as well as that of analogous molecules such as carbodicarbenes, carbon suboxide, and mixed systems. This chapter reviews theoretical and experimental research on carbodiphosphoranes C(PR3)2 and related compounds of formula C(L)2 as both, free molecules and ligands in transition metal or main group coordination complexes. Special emphasis will be given to highlight the unique reactivity derived from localizing two electron pairs at the same carbon atom.


Carbodicarbenes Carbodiphosphorane Catalysis Coordination chemistry Ligand design Main group chemistry 


  1. 1.
    Ramírez F, Desai NB, Hansen B, McKelvie N (1961) J Am Chem Soc 83:3539CrossRefGoogle Scholar
  2. 2.
    Kaska WC, Mitchell DK, Reichelderfer RF (1971) J Organomet Chem 47:391CrossRefGoogle Scholar
  3. 3.
    Vincent AT, Wheatley PJ (1972) J Chem Soc Dalton Trans 617Google Scholar
  4. 4.
    Hardy GE, Zink JI, Kaska WC, Baldwin JC (1978) J Am Chem Soc 100:8001CrossRefGoogle Scholar
  5. 5.
    Daly JJ, Wheatley PJ (1966) J Chem Soc A 1703Google Scholar
  6. 6.
    Birum GH, Matthews CN (1969) Acc Chem Res 2:373CrossRefGoogle Scholar
  7. 7.
    Schmidbaur H, Gasser O (1976) Angew Chem Int Ed Eng 15:502CrossRefGoogle Scholar
  8. 8.
    Bestmann HJ (1977) Angew Chem Int Ed Eng 16:349CrossRefGoogle Scholar
  9. 9.
    Schmidbaur H, Schier A (2013) Angew Chem Int Ed 52:176CrossRefGoogle Scholar
  10. 10.
    Petz W, Frenking G (2010) Top Organomet Chem 30:49CrossRefGoogle Scholar
  11. 11.
    Alcarazo M (2011, 1839) Dalton Trans 40Google Scholar
  12. 12.
    Frenking G, Hermann M, Andrada DM, Holzmann N (2016) Chem Soc Rev 45:1129CrossRefGoogle Scholar
  13. 13.
    Vicente J, Singhal AR, Jones PG (2002) Organometallics 21:5887CrossRefGoogle Scholar
  14. 14.
    Tonner R, Öxler F, Neumüller B, Petz W, Frenking G (2006) Angew Chem Int Ed 45:8038CrossRefGoogle Scholar
  15. 15.
    Tonner R, Frenking G (2008) Chem Eur J 14:3260CrossRefGoogle Scholar
  16. 16.
    Tonner R, Frenking G (2008) Chem Eur J 14:3273CrossRefGoogle Scholar
  17. 17.
    Alcarazo M, Lehmann CW, Anoop A, Thiel W, Fürstner A (2009) Nat Chem 1:295CrossRefGoogle Scholar
  18. 18.
    Viehe HC, Janousek Z, Gompper R, Lach D (1973) Angew Chem 85:581CrossRefGoogle Scholar
  19. 19.
    Dyker CA, Lavallo V, Donnadieu B, Bertrand G (2008) Angew Chem Int Ed 47:3206CrossRefGoogle Scholar
  20. 20.
    Fürstner A, Alcarazo M, Goddard R, Lehmann CW (2008) Angew Chem Int Ed 47:3210CrossRefGoogle Scholar
  21. 21.
    Kaufhold O, Hahn FE (2008) Angew Chem Int Ed 47:4507CrossRefGoogle Scholar
  22. 22.
    Hsu YC, Shen JS, Lin BC, Chen WC, Chan YT, Ching WM, Yap GPA, Hsu CP, Ong TG (2015) Angew Chem Int Ed 54:2420CrossRefGoogle Scholar
  23. 23.
    Chen WC, Shen JS, Jurca T, Peng CJ, Lin YH, Wang YP, Shih WC, Yap GPA, Ong TG (2015) Angew Chem Int Ed 54:15207CrossRefGoogle Scholar
  24. 24.
    Esterhuysen C, Frenking G (2011) Chem Eur J 17:9944CrossRefGoogle Scholar
  25. 25.
    Brown TJ, Sugie A, Leed MGD, Widenhoefer RA (2012) Chem Eur J 18:6959CrossRefGoogle Scholar
  26. 26.
    Tonner R, Frenking G (2007) Angew Chem Int Ed 46:8695CrossRefGoogle Scholar
  27. 27.
    Takagi N, Shimizu T, Frenking G (2009) Chem Eur J 15:3448CrossRefGoogle Scholar
  28. 28.
    Klein S, Tonner R, Frenking G (2010) Chem Eur J 16:10160CrossRefGoogle Scholar
  29. 29.
    Frenking G, Tonner R, Klein S, Takagi N, Shimizu T, Krapp A, Pandey KK, Parameswaran P (2014) Chem Soc Rev 43:5106CrossRefGoogle Scholar
  30. 30.
    Zhao L, Hermann M, Holzmann N, Frenking G (2017) Coord Chem Rev 344:163CrossRefGoogle Scholar
  31. 31.
    Gasser O, Schmidbaur H (1975) J Am Chem Soc 97:6281CrossRefGoogle Scholar
  32. 32.
    Hussain MS, Schmidbaur H (1976) Z Naturforsch 31b:721Google Scholar
  33. 33.
    Schmidbaur H, Hasslberger G, Deschler U, Schubert U, Kappenstein C, Frank A (1979) Angew Chem Int Ed Eng 18:408CrossRefGoogle Scholar
  34. 34.
    Appel R, Baumeister U, Knoch F (1983) Chem Ber 116:2275CrossRefGoogle Scholar
  35. 35.
    Schmidbaur H, Herr R, Zybill CE (1984) Chem Ber 117:3374CrossRefGoogle Scholar
  36. 36.
    Schmidbaur H, Nusstein P (1985) Organometallics 4:344CrossRefGoogle Scholar
  37. 37.
    Alcarazo M, Radkowski K, Mehler G, Goddard R, Fürstner A (2013) Chem Commun 49:3140CrossRefGoogle Scholar
  38. 38.
    Schmidbaur H, Costa T, Milewski-Mahrla B, Schubert U (1980) Angew Chem Int Ed Eng 19:555CrossRefGoogle Scholar
  39. 39.
    Schmidbaur H, Costa T (1981) Chem Ber 114:3063CrossRefGoogle Scholar
  40. 40.
    Bowmaker GA, Herr R, Schmidbaur H (1983) Chem Ber 116:3567CrossRefGoogle Scholar
  41. 41.
    Schmidbaur H, Herr R, Zybill CE (1984) Chem Ber 117:3380Google Scholar
  42. 42.
    Marrot S, Kato T, Gornitzka H, Baceiredo A (2006) Angew Chem 118:2660CrossRefGoogle Scholar
  43. 43.
    Pascual S, Asay M, Illa O, Kato T, Bertrand G, Saffon-Merceron N, Branchadell V, Baceiredo A (2007) Angew Chem Int Ed 46:9078CrossRefGoogle Scholar
  44. 44.
    Dellus N, Kato T, Bagán X, Saffon-Merceron N, Branchadell V, Baceiredo A (2010) Angew Chem Int Ed 49:6798CrossRefGoogle Scholar
  45. 45.
    Morosaki T, Suzuki T, Wang WW, Negase S, Fujii T (2014) Angew Chem Int Ed 53:9569CrossRefGoogle Scholar
  46. 46.
    Lavallo V, Dyker CA, Donnadieu B, Bertrand G (2008) Angew Chem Int Ed 47:5411CrossRefGoogle Scholar
  47. 47.
    Fernández I, Dyker CA, DeHope A, Donnadieu B, Frenking G, Bertrand G (2009) J Am Chem Soc 131:11875CrossRefGoogle Scholar
  48. 48.
    Christl M, Engels B (2009) Angew Chem Int Ed 48:1538CrossRefGoogle Scholar
  49. 49.
    Lavallo V, Dyker CA, Donnadieu B, Bertrand G (2009) Angew Chem Int Ed 48:1540CrossRefGoogle Scholar
  50. 50.
    Melaimi M, Parameswaran P, Donnadieu B, Frenking G, Bertrand G (2009) Angew Chem Int Ed 48:4792CrossRefGoogle Scholar
  51. 51.
    Panckevicious C, Liu L, Bertrand G, Stephan DW (2016) Angew Chem Int Ed 55:5536CrossRefGoogle Scholar
  52. 52.
    Gusev DG (2009) Organometallics 28:763CrossRefGoogle Scholar
  53. 53.
    Tolmann CA (1977) Chem Rev 77:313CrossRefGoogle Scholar
  54. 54.
    Denk K, Sirsch P, Herrmann WA (2002) J Organomet Chem 649:219CrossRefGoogle Scholar
  55. 55.
    Mayr M, Wurst K, Ongania KH, Buchmeiser MR (2004) Chem Eur J 10:1256CrossRefGoogle Scholar
  56. 56.
    Alcarazo M, Fernández R, Álvarez E, Lassaletta JM (2005) J Organomet Chem 690:5979CrossRefGoogle Scholar
  57. 57.
    Fürstner A, Alcarazo M, Radkowski K, Lehmann CW (2008) Angew Chem Int Ed 47:8302CrossRefGoogle Scholar
  58. 58.
    Tonner R, Frenking G (2009) Organometallics 28:3901CrossRefGoogle Scholar
  59. 59.
    Petz W, Weller F, Uddin J, Frenking G (1999) Organometallics 18:619CrossRefGoogle Scholar
  60. 60.
    Bent HA (1960) J Chem Educ 37:616CrossRefGoogle Scholar
  61. 61.
    Huheey JE (1981) Inorg Chem 20:4033CrossRefGoogle Scholar
  62. 62.
    Jonas V, Boehme C, Frenking G (1996) Inorg Chem 35:2097CrossRefGoogle Scholar
  63. 63.
    El-Hellani A, Monot J, Tang S, Guillot R, Bour C, Gandon V (2013) Inorg Chem 52:11493CrossRefGoogle Scholar
  64. 64.
    Inés B, Patil M, Carreras J, Goddard R, Thiel W, Alcarazo M (2011) Angew Chem Int Ed 50:8400CrossRefGoogle Scholar
  65. 65.
    Celik MA, Frenking G, Neumüller B, Petz W (2013) ChemPlusChem 78:1024CrossRefGoogle Scholar
  66. 66.
    Chen WC, Lee CY, Lin BC, Hsu YC, Shen JS, Hsu CP, Yap GPA, Ong TG (2014) J Am Chem Soc 136:914CrossRefGoogle Scholar
  67. 67.
    Tay MQY, Lu Y, Ganguly R, Vidović D (2013) Angew Chem Int Ed 52:3132CrossRefGoogle Scholar
  68. 68.
    Tay MQY, Ilić G, Werner-Zwanziger U, Lu Y, Ganguly R, Ricard L, Frison G, Carmichael D, Vidović D (2016) Organometallics 35:439CrossRefGoogle Scholar
  69. 69.
    Dordević N, Ganguly R, Petković M, Vidović D (2016) Chem Commun 52:9789CrossRefGoogle Scholar
  70. 70.
    Khan S, Gopakumar G, Thiel W, Alcarazo M (2013) Angew Chem Int Ed 52:5644CrossRefGoogle Scholar
  71. 71.
    Petz W, Dehnicke K, Holtzmann N, Frenking G, Neumüller B (2011) Z Anorg Allg Chem 637:1702CrossRefGoogle Scholar
  72. 72.
    Petz W, Kuzu I, Frenking G, Andrada DM, Neumüller B, Fritz M, Münzer JE (2016) Chem Eur J 22:8536CrossRefGoogle Scholar
  73. 73.
    Kuhn N, Bohnen H, Fahl J, Blaeser D, Boese R (1996) Chem Ber 129:1579CrossRefGoogle Scholar
  74. 74.
    Kuhn N, Abu-Rayyan A, Eichele K, Piludu C, Steimann M (2004) Z Anorg Allg Chem 630:495CrossRefGoogle Scholar
  75. 75.
    Kuhn N, Abu-Rayyan A, Ströbele M (2002) Z Anorg Allg Chem 628:2251CrossRefGoogle Scholar
  76. 76.
    Arduengo AJ, Tamm M, Calabrese JC (1994) J Am Chem Soc 116:3625CrossRefGoogle Scholar
  77. 77.
    Schmidbaur H, Zybill C, Neugebauer D, Müller G (1985) Z Naturforsch 40:1293Google Scholar
  78. 78.
    Petz W, Heimann S, Öxler F, Neumüller B (2007) Z Anorg Allg Chem 633:365CrossRefGoogle Scholar
  79. 79.
    Inés B, Holle S, Goddard R, Alcarazo M (2010) Angew Chem Int Ed 49:8389CrossRefGoogle Scholar
  80. 80.
    Palomas D, Holle S, Inés B, Bruns H, Goddard R, Alcarazo M (2012) Dalton Trans 41:9073CrossRefGoogle Scholar
  81. 81.
    Petz W, Öxler F, Neumüller B, Tonner R, Frenking G (2009) Eur J Inorg Chem 4507Google Scholar
  82. 82.
    Bianchini C, Meli A, Orlandini A, Sacconi L (1980) Angew Chem 92:1055CrossRefGoogle Scholar
  83. 83.
    Bianchini C, Meli A, Orlandini A, Sacconi L (1981) J Organomet Chem 218:81CrossRefGoogle Scholar
  84. 84.
    Schmidbaur H, Zybill CE, Neugebauer D (1982) Angew Chem 94:321CrossRefGoogle Scholar
  85. 85.
    Petz W, Neumüller B (2011) Eur J Inorg Chem 4889Google Scholar
  86. 86.
    Petz W, Neumüller B, Klein S, Frenking G (2011) Organometallics 30:3330CrossRefGoogle Scholar
  87. 87.
    Zybill C, Müller G (1987) Organometallics 6:2489CrossRefGoogle Scholar
  88. 88.
    Pranckevicius C, Iovan DA, Stephan DW (2016) Dalton Trans 45:16820CrossRefGoogle Scholar
  89. 89.
    Corberán R, Marrot S, Dellus N, Merceron-Saffon N, Kato T, Peris E, Baceiredo A (2009) Organometallics 28:326CrossRefGoogle Scholar
  90. 90.
    DeHope A, Donnadieu B, Bertrand G (2011) J Organomet Chem 696:2899CrossRefGoogle Scholar
  91. 91.
    Sundermeyer J, Weber K, Peters K, von Schnering HG (1994) Organometallics 13:2560CrossRefGoogle Scholar
  92. 92.
    Toreki R, Schrock RR, Davis WM (1992) J Am Chem Soc 114:3367CrossRefGoogle Scholar
  93. 93.
    Reitsamer C, Shuh W, Kopacka H, Wurst K, Ellmerer EP, Peringer P (2011) Organometallics 30:4220CrossRefGoogle Scholar
  94. 94.
    Reitsamer C, Schuh W, Kopacka H, Wurst K, Peringer P (2009) Organometallics 28:6617CrossRefGoogle Scholar
  95. 95.
    Kubo K, Okitsu H, Miwa H, Kume S, Cavell RG, Mizuta T (2017) Organometallics 36:266CrossRefGoogle Scholar
  96. 96.
    Alcarazo M, Gomez C, Holle S, Goddard R (2010) Angew Chem Int Ed 49:5788CrossRefGoogle Scholar
  97. 97.
    Dobrovetsky R, Stephan DW (2013) Angew Chem Int Ed 52:2516CrossRefGoogle Scholar
  98. 98.
    El-Hellani A, Bour C, Gandon V (2011) Adv Synth Catal 353:1865CrossRefGoogle Scholar
  99. 99.
    Alcarazo M, Stork T, Anoop A, Thiel W, Fürstner A (2010) Angew Chem Int Ed 49:2542CrossRefGoogle Scholar
  100. 100.
    Pranckevicious C, Fan L, Stephan DW (2015) J Am Chem Soc 137:5582CrossRefGoogle Scholar
  101. 101.
    Goldfogel MJ, Roberts CC, Meek SJ (2014) J Am Chem Soc 136:6227CrossRefGoogle Scholar
  102. 102.
    Roberts CC, Matías DM, Goldfogel MJ, Meek SJ (2015) J Am Chem Soc 137:6488CrossRefGoogle Scholar
  103. 103.
    Goldfogel MJ, Roberts CC, Manan RS, Meek SJ (2017) Org Lett 19:90CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Institut für Organische und Biomolekulare ChemieGeorg-August-Universität GöttingenGöttingenGermany

Personalised recommendations