The Role of NHC Ligands in Oxidation Catalysis

Chapter
Part of the Topics in Organometallic Chemistry book series (TOPORGAN, volume 22)

Abstract

During the last decade N-heterocyclic carbenes (NHC) have become a very important class of ligands for catalytic applications. They have been employed in reactions like C-C/C-N coupling, olefin metathesis, hydrosilylation and hydrogenation. Recently, also in the field of oxidation catalysis significant progress has been achieved. NHC ligands are known to efficiently activate metal centers and they are surprisingly resistant, even in acidic media. In contrast to phosphine ligands, the metal-NHC bond is also stable under oxidizing conditions. This review covers the oxidation of organic substrates by NHC catalysts as well as the fixation and activation of O2 and CO2 by NHC complexes. A variety of oxidation reactions have been studied using NHC catalysts, but the oxidation of alcohols and olefins was of particular interest. Most of the work in this area was conducted with palladium catalysts, which even allow the efficient oxidation of alcohols at ambient temperature using molecular oxygen. Bi- and tridentate NHC ligands are described as well as a variety of complexes with different metals other than palladium. Reactive intermediates like peroxo complexes have been characterized experimentally, while DFT calculations have been used to explain the mechanisms of the oxidation chemistry of transition metal NHC complexes.

Catalysis DFT calculations N-heterocyclic carbenes Oxidation Palladium 

Abbreviations

acac

acetylacetonate

BDE

bond dissociation energy

CDA

charge decomposition analysis

CNC

2,6-bis(butylimidazole-2-ylidene)pyridine

Cp

cyclopentadienyl

Cy

cyclohexyl

DFT

density functional theory

EDA

energy decomposition analysis

Hal

halogen

HF

Hartree–Fock

Me

methyl

NHC

N-heterocyclic carbene

OAc

acetate

Ph

phenyl

PPh3

triphenylphosphine

post-HF

post-Hartree–Fock

TM

transition metal

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References

  1. 1.
    Doering WvE, Hoffmann AK (1954) J Am Chem Soc 76:6162 Google Scholar
  2. 2.
    Fischer EO, Maasboel A (1964) Angew Chem 76:645 Google Scholar
  3. 3.
    Fischer EO (1974) Angew Chem 86:651 Google Scholar
  4. 4.
    Igau A, Grutzmacher H, Baceiredo A, Bertrand G (1988) J Am Chem Soc 110:6463 Google Scholar
  5. 5.
    Bourissou D, Bertrand G (1999) Adv Organomet Chem 44:175 CrossRefGoogle Scholar
  6. 6.
    Arduengo AJ III, Harlow RL, Kline M (1991) J Am Chem Soc 113:2801 Google Scholar
  7. 7.
    Arduengo AJ III, Harlow RL, Kline M (1991) J Am Chem Soc 113:361 Google Scholar
  8. 8.
    Arduengo AJ III (1999) Accounts Chem Res 32:913 Google Scholar
  9. 9.
    Arduengo AJ III, Davidson F, Dias HVR, Goerlich JR, Khasnis D, Marshall WJ, Prakasha TK (1997) J Am Chem Soc 119:12742 Google Scholar
  10. 10.
    Fischer J (1996) Dissertation, Technische Universität München, Germany Google Scholar
  11. 11.
    Wanzlick HW, Schoenherr HJ (1968) Angew Chem Int Ed Engl 7:141 Google Scholar
  12. 12.
    Oefele K (1968) J Organomet Chem 12:P42 Google Scholar
  13. 13.
    Schrock RR (1974) J Am Chem Soc 96:6796 Google Scholar
  14. 14.
    Koecher C, Herrmann WA (1997) J Organomet Chem 532:261 Google Scholar
  15. 15.
    Herrmann WA, Goossen LJ, Artus GRJ, Koecher C (1997) Organometallics 16:2472 Google Scholar
  16. 16.
    Herrmann WA, Goossen LJ, Koecher C, Artus GRJ (1997) Angew Chem Int Ed Engl 35:2805 Google Scholar
  17. 17.
    Herrmann WA, Koecher C, Goossen LJ, Artus GRJ (1996) Chem A Eur J 2:1627 Google Scholar
  18. 18.
    Herrmann WA, Elison M, Fischer J, Koecher C, Artus GRJ (1996) Chem A Eur J 2:772 Google Scholar
  19. 19.
    Herrmann WA, Elison M, Fischer J, Koecher C, Artus GRJ (1995) Angew Chem Int Ed Engl 34:2371 Google Scholar
  20. 20.
    Denk MK, Thadani A, Hatano K, Lough AJ (1997) Angew Chem Int Ed Engl 36:2607 Google Scholar
  21. 21.
    Alder RW, Blake ME, Bortolotti C, Bufali S, Butts CP, Linehan E, Oliva JM, Orpen AG, Quayle MJ (1999) Chem Commun (Cambridge), p 1049 Google Scholar
  22. 22.
    Alder RW, Blake ME, Bortolotti C, Bufali S, Butts CP, Linehan E, Oliva JM, Orpen AG, Quayle MJ (1999) Chem Commun (Cambridge), p 241 Google Scholar
  23. 23.
    Alder RW, Blake ME (1997) Chem Commun (Cambridge), p 1513 Google Scholar
  24. 24.
    Alder RW, Allen PR, Murray M, Orpen AG (1996) Angew Chem Int Ed Engl 35:1121 Google Scholar
  25. 25.
    Scarborough CC, Popp BV, Guzei IA, Stahl SS (2005) J Organomet Chem 690:6143 Google Scholar
  26. 26.
    Scarborough CC, Grady MJW, Guzei IA, Gandhi BA, Bunel EE, Stahl SS (2005) Angew Chem Int Ed 44:5269 Google Scholar
  27. 27.
    Altenhoff G, Goddard R, Lehmann Christian W, Glorius F (2004) J Am Chem Soc 126:15195 Google Scholar
  28. 28.
    Altenhoff G, Goddard R, Lehmann Christian W, Glorius F (2003) Angew Chem Int Ed 42:3690 Google Scholar
  29. 29.
    Herrmann WA, Weskamp T, Bohm VPW (2001) Adv Organomet Chem 48:1 Google Scholar
  30. 30.
    Weskamp T, Bohm VPW, Herrmann WA (2000) J Organomet Chem 600:12 Google Scholar
  31. 31.
    Herrmann WA (2002) Angew Chem Int Ed 41:1290 Google Scholar
  32. 32.
    Wanzlick HW (1962) Angew Chem 74:129 Google Scholar
  33. 33.
    Arduengo AJ III, Dias HVR, Dixon DA, Harlow RL, Klooster WT, Koetzle TF (1994) J Am Chem Soc 116:6812 Google Scholar
  34. 34.
    Arduengo AJ III, Goerlich JR, Marshall WJ (1995) J Am Chem Soc 117:11027 Google Scholar
  35. 35.
    Lehmann JF, Urquhart SG, Ennis LE, Hitchcock AP, Hatano K, Gupta S, Denk MK (1999) Organometallics 18:1862 Google Scholar
  36. 36.
    Boehme C, Frenking G (1996) J Am Chem Soc 118:2039 Google Scholar
  37. 37.
    Boehme C, Frenking G (1998) Organometallics 17:5801 Google Scholar
  38. 38.
    Heinemann C, Mueller T, Apeloig Y, Schwarz H (1996) J Am Chem Soc 118:2023 Google Scholar
  39. 39.
    McGuinness DS, Yates BF, Cavell KJ (2002) Organometallics 21:5408 Google Scholar
  40. 40.
    Gleiter R, Hoffmann R (1968) J Am Chem Soc 90:5457 Google Scholar
  41. 41.
    Dixon DA, Arduengo AJ III (1991) J Phys Chem 95:4180 Google Scholar
  42. 42.
    Cioslowski J (1993) Int J Quantum Chem, Quantum Chem Symposium 27:309 Google Scholar
  43. 43.
    Kutzelnigg W (1984) Angew Chem 96:262 Google Scholar
  44. 44.
    Gobbi A, Frenking G (1994) J Am Chem Soc 116:9287 Google Scholar
  45. 45.
    Kutzelnigg W (1980) Israel J Chem 19:193 Google Scholar
  46. 46.
    Schindler M, Kutzelnigg W (1982) J Chem Phys 76:1919 Google Scholar
  47. 47.
    Hansen AE, Bouman TD (1985) J Chem Phys 82:5035 Google Scholar
  48. 48.
    Heinemann C, Thiel W (1994) Chem Phys Lett 217:11 Google Scholar
  49. 49.
    Schmidt B (2003) Angew Chem Int Ed 42:4996 Google Scholar
  50. 50.
    Schwab P, Grubbs RH, Ziller JW (1996) J Am Chem Soc 118:100 Google Scholar
  51. 51.
    Schwab P, France MB, Ziller JW, Grubbs RH (1995) Angew Chem Int Ed Engl 34:2039 Google Scholar
  52. 52.
    Nguyen ST, Grubbs RH, Ziller JW (1993) J Am Chem Soc 115:9858 Google Scholar
  53. 53.
    Weskamp T, Schattenmann WC, Spiegler M, Herrmann WA (1998) Angew Chem Int Ed Engl 37:2490 Google Scholar
  54. 54.
    Zeller A, Herdtweck E, Strassner T (2005) Acta Crystallograph C: Cryst Struct Commun C61:m46 Google Scholar
  55. 55.
    Muehlhofer M, Strassner T, Herrmann WA (2002) Angew Chem Int Ed 41:1745 Google Scholar
  56. 56.
    Maletz G, Schmidt F, Reimer A, Strassner T, Muehlhofer M, Mihalios D, Herrmann W (2003) Ger Offen (Sued-Chemie AG, Germany) De, p 10 Google Scholar
  57. 57.
    Ahrens S, Herdtweck E, Goutal S, Strassner T (2006) Eur J Inorg Chem 6:1268 Google Scholar
  58. 58.
    Muehlhofer M, Strassner T, Herdtweck E, Herrmann WA (2002) J Organomet Chem 660:121 Google Scholar
  59. 59.
    Strassner T, Muehlhofer M, Zeller A, Herdtweck E, Herrmann WA (2004) J Organomet Chem 689:1418 Google Scholar
  60. 60.
    Viciano M, Poyatos M, Sanau M, Peris E, Rossin A, Ujaque G, Lledos A (2006) Organometallics 25:1120 Google Scholar
  61. 61.
    Duin MA, Clement ND, Cavell KJ, Elsevier CJ (2003) Chem Commun (Cambridge), p 400 Google Scholar
  62. 62.
    Clement Nicolas D, Cavell Kingsley J, Jones C, Elsevier Cornelis J (2004) Angew Chem Int Ed 43:1277 Google Scholar
  63. 63.
    McGuinness DS, Cavell KJ, Yates BF, Skelton BW, White AH (2001) J Am Chem Soc 123:8317 Google Scholar
  64. 64.
    McGuinness DS, Yates BF, Cavell KJ (2001) Chem Commun (Cambridge), p 355 Google Scholar
  65. 65.
    Clement ND, Cavell KJ (2004) Angew Chem Int Ed 43:3845 Google Scholar
  66. 66.
    Hawkes KJ, McGuinness DS, Cavell KJ, Yates BF (2004) Dalton Trans, p 2505 Google Scholar
  67. 67.
    Bacciu D, Cavell Kingsley J, Fallis Ian A, Ooi L-L (2005) Angew Chem Int Ed 44:5282 Google Scholar
  68. 68.
    Rubio RJ, Andavan GTS, Bauer EB, Hollis TK, Cho J, Tham FS, Donnadieu B (2005) J Organomet Chem 690:5353 Google Scholar
  69. 69.
    Wang HMJ, Lin IJB (1998) Organometallics 17:972 Google Scholar
  70. 70.
    Garrison JC, Youngs WJ (2005) Chem Rev (Washington, DC) 105:3978 Google Scholar
  71. 71.
    Royo B, Herdtweck E, Romao CC (2004) Eur J Inorg Chem, p 3305 Google Scholar
  72. 72.
    Kueckmann TI, Abram U (2004) Inorg Chem 43:7068 Google Scholar
  73. 73.
    Evans WJ, Kozimor SA, Ziller JW (2004) Polyhedron 23:2689 Google Scholar
  74. 74.
    Hu X, Castro-Rodriguez I, Meyer K (2004) J Am Chem Soc 126:13464 Google Scholar
  75. 75.
    Dible BR, Sigman MS (2003) J Am Chem Soc 125:872 Google Scholar
  76. 76.
    Dible BR, Sigman MS, Arif AM (2005) Inorg Chem 44:3774 Google Scholar
  77. 77.
    Yamashita M, Goto K, Kawashima T (2005) J Am Chem Soc 127:7294 Google Scholar
  78. 78.
    Konnick MM, Guzei IA, Stahl SS (2004) J Am Chem Soc 126:10212 Google Scholar
  79. 79.
    Okuyama K-I, Sugiyama J-I, Nagahata R, Asai M, Ueda M, Takeuchi K (2003) Macromolecules 36:6953 Google Scholar
  80. 80.
    Okuyama K-i, Sugiyama J-i, Nagahata R, Asai M, Ueda M, Takeuchi K (2003) J Mol Catal A: Chem 203:21 Google Scholar
  81. 81.
    Muzart J (2005) Tetrahedron 61:9423 Google Scholar
  82. 82.
    Muzart J (2005) Tetrahedron 61:5955 Google Scholar
  83. 83.
    Muzart J (2005) Tetrahedron 61:4179 Google Scholar
  84. 84.
    Muzart J (2003) Tetrahedron 59:5789 Google Scholar
  85. 85.
    Nishimura T, Maeda Y, Kakiuchi N, Uemura S (2000) J Chem Soc Perkin Trans 1:4301 Google Scholar
  86. 86.
    Nishimura T, Kakiuchi N, Onoue T, Ohe K, Uemura S (2000) J Chem Soc Perkin Trans 1:1915 Google Scholar
  87. 87.
    Nishimura T, Onoue T, Ohe K, Uemura S (1999) J Org Chem 64:6750 Google Scholar
  88. 88.
    ten Brink G-j, Arends IWCE, Sheldon RA (2000) Science (Washington, DC) 287:1636 Google Scholar
  89. 89.
    Jensen DR, Schultz MJ, Mueller JA, Sigman MS (2003) Angew Chem Int Ed 42:3810 Google Scholar
  90. 90.
    Mueller JA, Goller CP, Sigman MS (2004) J Am Chem Soc 126:9724 Google Scholar
  91. 91.
    Schultz MJ, Hamilton SS, Jensen DR, Sigman MS (2005) J Org Chem 70:3343 Google Scholar
  92. 92.
    Muniz K (2004) Adv Synth Catal 346:1425 Google Scholar
  93. 93.
    Keith JM, Nielsen RJ, Oxgaard J, Goddard WA III (2005) J Am Chem Soc 127:13172 Google Scholar
  94. 94.
    Nielsen RJ, Keith JM, Stoltz BM, Goddard WA III (2004) J Am Chem Soc 126:7967 Google Scholar
  95. 95.
    Privalov T, Linde C, Zetterberg K, Moberg C (2005) Organometallics 24:885 Google Scholar
  96. 96.
    Keith JA, Oxgaard J, Goddard WA III (2006) J Am Chem Soc 128:3132 Google Scholar
  97. 97.
    Jensen DR, Sigman MS (2003) Org Lett 5:63 Google Scholar
  98. 98.
    Nicholas KM, Ferreira EM, Stoltz BM, Jensen DR, Pugsley JS, Sigman MS (2001) Chemtracts 14:654 Google Scholar
  99. 99.
    Ferreira EM, Stoltz BM (2001) J Am Chem Soc 123:7725 Google Scholar
  100. 100.
    Lebel H, Paquet V (2004) J Am Chem Soc 126:11152 Google Scholar
  101. 101.
    Hanasaka F, Fujita K-i, Yamaguchi R (2004) Organometallics 23:1490 Google Scholar
  102. 102.
    Hanasaka F, Fujita K, Yamaguchi R (2005) Organometallics 24:3422 Google Scholar
  103. 103.
    Mizushima E, Sato K, Hayashi T, Tanaka M (2002) Angew Chem Int Ed 41:4563 Google Scholar
  104. 104.
    Teles JH, Brode S, Chabanas M (1998) Angew Chem Int Ed Engl 37:1415 Google Scholar
  105. 105.
    Schneider SK, Herrmann WA, Herdtweck E (2003) Zeitschr Anorg Allgem Chem 629:2363 Google Scholar
  106. 106.
    Poyatos M, Mata JA, Falomir E, Crabtree RH, Peris E (2003) Organometallics 22:1110 Google Scholar
  107. 107.
    Robinson SD, Levison JJ (1970) J Chem Soc [Section] A: Inorganic, Physical, Theoretical, p 2947 Google Scholar
  108. 108.
    Cornell CN, Sigman MS (2005) J Am Chem Soc 127:2796 Google Scholar
  109. 109.
    Ramirez J, Corberan R, Sanau M, Peris E, Fernandez E (2005) Chem Commun (Cambridge), p 3056 Google Scholar
  110. 110.
    Jia C, Kitamura T, Fujiwara Y (2001) Acc Chem Res 34:633 Google Scholar
  111. 111.
    Periana RA, Taube DJ, Gamble S, Taube H, Satoh T, Fujii H (1998) Science (Washington, DC) 280:560 Google Scholar
  112. 112.
    Gol'dshleger NF, Tyabin MB, Shilov AE, Shteinman AA (1969) Zh Fiz Khim 43:2174 Google Scholar
  113. 113.
    Wolf D (1998) Angew Chem Int Ed Engl 37:3351 Google Scholar
  114. 114.
    Crabtree RH (1995) Chem Rev 95:987 Google Scholar
  115. 115.
    Stahl S, Labinger JA, Bercaw JE (1998) Angew Chem Int Ed Engl 37:2181 Google Scholar
  116. 116.
    Lin M, Sen A (1994) Nature (London) 368:613 Google Scholar
  117. 117.
    Taniguchi Y, Hayashida T, Shibasaki H, Piao D, Kitamura T, Yamaji T, Fujiwara Y (1999) Org Lett 1:557 Google Scholar
  118. 118.
    Asadullah M, Taniguchi Y, Kitamura T, Fujiwara Y (2000) Appl Catal A 194–195:443 Google Scholar
  119. 119.
    Nakata K, Yamaoka Y, Miyata T, Taniguchi Y, Takaki K, Fujiwara Y (1994) J Organomet Chem 473:329 Google Scholar
  120. 120.
    Herdtweck E, Muehlhofer M, Strassner T (2003) Acta Crystallogr E: Structure Reports Online E59:m970 Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2006

Authors and Affiliations

  1. 1.Technische Universität DresdenPhysikalische Organische ChemieDresdenGermany

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