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Oxidative Addition Reactions

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Theoretical Aspects of Homogeneous Catalysis

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 18))

Abstract

Two-electron oxidative addition reactions are defined by equation (1). In this reaction where the A-B bond is activated, the metal center M is formally oxidized by two units as the two new M-A and M-B bonds are formed. The reverse reaction, the formation of the A-B bond, is termed reductive elimination. These two elementary reactions are common in organometallic reactions and they constitute significant steps in many catalytic cycles. An important example of reaction 1 is the oxidative addition of the H2 molecule, which is an obligatory step in many catalytic cycles, such as hydrogenation of unsaturated hydrocarbons, hydroformylation and the reductive oligomerizationof carbon monoxide [1]. The similarity between the H-H and the alkane C-H bonds, which are about equal in bond strengths and polarities, suggest that the oxidative addition might be a possible route for the activation of alkanes. Since alkanes are so abundant, they are very attractive as raw material for the synthesis of more useful organic molecules and therefore the search for effective and selective methods to activate this unreactive class of molecules have had high priority in chemical research for many years. A large number of theoretical studies have also been performed to elucidate the mechanisms of alkane activation. In this chapter a review is given of the most recent results obtained from studies of oxidative addition to transition metal centers.

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References

  1. J.P. Collman, L.S. Hegedus, J.R. Norton and R.G. Finke: Principles and Applications of Organotransition Metal Chemistry. University Science Books (1987), Mill Valley

    Google Scholar 

  2. J. Chatt and J.M. Davidson, J. Chem. Soc. 1965, 843

    Google Scholar 

  3. W.D. Jones and F.J. Feher, Acc. Chem. Res. 22, 91 (1989)

    Article  CAS  Google Scholar 

  4. (a) A.H. Janowicz and R.G. Bergman, J. Am. Chem. Soc. 104,352 (1982)

    Article  CAS  Google Scholar 

  5. A.H. Janowicz and R.G. Bergman, J. Am. Chem. Soc. 105, 3929 (1983)

    Article  CAS  Google Scholar 

  6. (a) J.K. Hoyano and W.A.G. Graham, J. Am. Chem. Soc. 104,3723 (1982)

    Article  CAS  Google Scholar 

  7. J.K. Hoyano, A.D. McMaster and W.A.G. Graham, J. Am. Chem. Soc. 105, 7190 (1983)

    Article  CAS  Google Scholar 

  8. (a) W.D. Jones and F.J. Feher, J. Am. Chem. Soc. 104, 4240 (1982)

    Article  CAS  Google Scholar 

  9. W.D. Jones and F.J. Feher, J. Am. Chem. Soc. 106, 1650 (1984)

    Article  CAS  Google Scholar 

  10. T. Sakakura, T. Sodeyama, K. Sasaki, K. Wada and M. Tanaka, J. Am. Chem. Soc. 112, 7221 (1990)

    Article  CAS  Google Scholar 

  11. Perspectives in the Selective Activation of C-H and C-C Bonds in Saturated Hydrocarbons, B. Meunier and B. Chaudret, Ed., Scientific Affairs Division -NATO (1988), Brussels

    Google Scholar 

  12. A.J. Rest, I. Whitwell, W.A.G. Graham, J.K. Hoyano andA.D.J. McMaster, Chem. Soc. Chem. Commun. 1984, 624

    Google Scholar 

  13. D.M. Haddleton,A. McCamley and R.N. Perutz, J. Am. Chem. Soc. 110, 1810(1988)

    Article  CAS  Google Scholar 

  14. S.T. Belt, F.-W. Grevels, W.E. Klotzbücher, A. McCamley and R.N. Perutz, J. Am. Chem. Soc. 111,8373 (1989)

    Article  CAS  Google Scholar 

  15. J. Halpern, Inorganica Chimica Acta 100, 41 (1985)

    Article  CAS  Google Scholar 

  16. P.O. Stoutland and R.G. Bergman, J. Am. Chem. Soc. 107, 4581 (1985)

    Article  CAS  Google Scholar 

  17. P.O. Stoutland and R.G. Bergman, J. Am. Chem. Soc. 110, 5732 (1988)

    Article  CAS  Google Scholar 

  18. M.V. Baker and L.D. Field, J.Am. Chem. Soc. 108,7433 (1986)

    Article  CAS  Google Scholar 

  19. M.V. Baker and L.D. Field, J.Am. Chem. Soc. 108,7436 (1986)

    Article  CAS  Google Scholar 

  20. T.T. Wenzel and R.G. Bergman, J.Am. Chem. Soc. 108,4856(1986)

    Article  CAS  Google Scholar 

  21. W.D. Jones, R.M. Chin, L. Dong, S.B. Duckett and E.T. Hessell, In Energetics of Organometallic Species, Simões, J.A.M., Ed., Kluwer (1992), Dordrecht, pp. 54-67

    Google Scholar 

  22. C.F.H. Tipper, J. Chem. Soc. 1955, 2045

    Google Scholar 

  23. D.M. Adams, J. Chatt, R. Guy and N. Sheppard, J. Chem. Soc. 1961, 738

    Google Scholar 

  24. R.H. Crabtree, Chem. Rev. 85, 245 (1985)

    Article  CAS  Google Scholar 

  25. (a) Z.H. Kafafi, In Selective Hydrocarbon Activation: Principles and Progress, J.A. Davies, P.L. Watson, A. Greenberg and J.F. Liebman, Ed., VCH Publishers (1990), New York, pp. 411-132

    Google Scholar 

  26. E.S. Kline, R.H. Hauge, Z.H. Kafafí and J.L. Margrave, Organometallics 7, 1512 (1988)

    Article  CAS  Google Scholar 

  27. (a) K.J. Klabunde andY. Tanaka, J.Am. Chem. Soc. 105, 3544 (1983)

    Article  CAS  Google Scholar 

  28. K.J. Klabunde, Gi Ho Jeong and A.W. Olsen, In Selective Hydrocarbon Activation: Principles and Progress, J.A. Davies, P.L. Watson, A. Greenberg and J.F. Liebman, Ed., VCH Publishers (1990), New York, pp. 433-66

    Google Scholar 

  29. D. Ritter and J.C. Weisshaar, J. Am. Chem. Soc. 112, 6425 (1990)

    Article  CAS  Google Scholar 

  30. S.A. Mitchell and P.A. Hackett, J. Chem. Phys. 93, 7822 (1990)

    Article  CAS  Google Scholar 

  31. (a) J.C. Weisshaar, Advances in Chem. Phys. 81

    Google Scholar 

  32. J.C. Weisshaar, Ch.13 in Gas-Phase Metal Reactions, A. Fontijn, Ed., Elsevier (1992), Amsterdam

    Google Scholar 

  33. P.B. Armentrout and J.L. Beauchamp, Acc. Chem. Res. 22,315(1989)

    Article  CAS  Google Scholar 

  34. P.B. Armentrout, In Selective Hydrocarbon Activation: Principles and Progress, J.A. Davies,P.L. Watson, A. Greenberg and J.F. Liebman, Ed., VCH Publishers (1990), New York, pp. 467-533

    Google Scholar 

  35. P.A.M. van Koppen, M.T. Bowers, J.L. Beachaump and D.V. Dearden, In Bonding Energetics in Organometallic Compounds, T.J. Marks, Ed., ACS Symposium Series (1990), Washington DC, pp. 34-54

    Chapter  Google Scholar 

  36. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, J. Am. Chem. Soc. 114, 6095 (1992)

    Article  CAS  Google Scholar 

  37. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, J. Phys. Chem. 96, 9794 (1992)

    Article  CAS  Google Scholar 

  38. P.E.M. Siegbahn and M.R.A. Blomberg, J. Am. Chem. Soc. 114, 10548 (1992)

    Article  CAS  Google Scholar 

  39. P.E.M. Siegbahn, M.R.A. Blomberg and M. Svensson, J. Am. Chem. Soc. 115, 1952 (1993)

    Article  CAS  Google Scholar 

  40. P.E.M. Siegbahn, M.R.A. Blomberg and M. Svensson, J. Am. Chem. Soc. 115, 4191 (1993)

    Article  CAS  Google Scholar 

  41. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, 32, 4218 (1993) Inorg. Chem

    Article  CAS  Google Scholar 

  42. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, J. Phys. Chem. 97, 2564 (1993)

    Article  Google Scholar 

  43. P.E.M. Siegbahn, Theor. Chim. Acta 86, 219 (1993)

    Article  CAS  Google Scholar 

  44. P.E.M. Siegbahn, Chem. Phys. Letters 201, 15 (1993)

    Article  CAS  Google Scholar 

  45. P.E.M. Siegbahn, Theor. Chim. Acta 87, 441 (1994)

    Article  CAS  Google Scholar 

  46. P.E.M. Siegbahn, J. Am. Chem. Soc. 115, 5803(1993)

    Article  CAS  Google Scholar 

  47. P.E.M. Siegbahn, Theor. Chim. Acta. 87, 277 (1994)

    Article  CAS  Google Scholar 

  48. P.E.M. Siegbahn, Chem. Phys. Letters 205, 290 (1993)

    Article  CAS  Google Scholar 

  49. M.R.A. Blomberg, C.A.M. Karlsson and P.E.M. Siegbahn, J. Phys. Chem. 97, 9341 (1993)

    Article  CAS  Google Scholar 

  50. P.E.M. Siegbahn, J. Phys. Chem. 97, 9096 (1993)

    Article  CAS  Google Scholar 

  51. (a) S.R. Langhoff, L.G.M. Pettersson and C.W. Bauschlicher, Jr., J. Chem. Phys. 86, 268 (1987)

    Article  CAS  Google Scholar 

  52. C.W. Bauschlicher, Jr., S.R. Langhoff, H. Partridge and L.A. Barnes, J. Chem. Phys. 91, 2399 (1989)

    Article  CAS  Google Scholar 

  53. M. Rosi, C.W. Bauschlicher, Jr., S.R. Langhoff and H. Partridge, J. Phys. Chem. 94, 8656 (1990)

    Article  CAS  Google Scholar 

  54. M. Rosi, C.W Bauschlicher, Jr. Chem. Phys. Lett. 166, 189 (1990)

    Article  CAS  Google Scholar 

  55. (e) C.W. Bauschlicher, Jr. and S.R.Langhoff, J. Phys. Chem. 95, 2278 (1991)

    Article  CAS  Google Scholar 

  56. M. Sodupe, C.W. Bauschlicher, Jr., S.R. Langhoff and H. Partridge, J. Phys. Chem. 96, 2118 (1992)

    Article  CAS  Google Scholar 

  57. (a)K. Balasubramanian and C. Ravimohan, Chem. Phys. Lett. 145, 39 (1988)

    Article  CAS  Google Scholar 

  58. (b) K. Balasubramanian and C. Ravimohan, J. Phys. Chem. 93, 4490 (1989)

    Article  CAS  Google Scholar 

  59. K. Balasubramanian and J.Z. Wang, J. Chem. Phys. 91, 7761 (1989)

    Article  CAS  Google Scholar 

  60. K. Balasubramanian and D.W.Liao, J. Phys. Chem. 92,6259 (1988)

    Article  CAS  Google Scholar 

  61. J.Z. Wang, K.K. Das and K. Balasubramanian, Mol. Phys. 69, 147 (1990)

    Article  CAS  Google Scholar 

  62. J. Li and K. Balasubramanian, J. Phys. Chem. 94, 545 (1990)

    Article  CAS  Google Scholar 

  63. K. Balasubramanian, P.Y. Feng and M.Z. Liao, J. Chem. Phys. 88, 6955 (1988)

    Article  CAS  Google Scholar 

  64. E.A. Carter and W.A. Goddard III, J. Phys. Chem. 92, 5679 (1988)

    Article  CAS  Google Scholar 

  65. M. Blomberg, U. Brandemark, L. Pettersson and P. Siegbahn, Int. J. Quantum. Chem. XXIII, 855(1983)

    Article  Google Scholar 

  66. M.R.A. Blomberg, U. Brandemark and P.E.M. Siegbahn, J. Am. Chem. Soc. 105,5557 (1983)

    Article  CAS  Google Scholar 

  67. J.J. Low and W.A. Goddard III, J. Am. Chem. Soc. 106, 8321 (1984)

    Article  CAS  Google Scholar 

  68. J.J. Low and W.A. Goddard III, Organometallics 5, 609(1986)

    Article  CAS  Google Scholar 

  69. J.J. Low and W.A. Goddard III, J. Am. Chem. Soc. 106, 6928 (1984)

    Article  CAS  Google Scholar 

  70. J.J. Low and W.A. Goddard III, J. Am. Chem. Soc. 108, 6115 (1986)

    Article  CAS  Google Scholar 

  71. N. Koga and K. Morokuma, Chem. Rev. 91, 823 (1991)

    Article  CAS  Google Scholar 

  72. P.J. Hay, In Transition Metal Hydrides, A. Dedieu, Ed., VCH Publishers (1992), New York, pp. 127-147

    Google Scholar 

  73. K. Kitaura, S. Obara and K. Morokuma, J. Am. Chem. Soc. 103, 2891 (1981)

    Article  CAS  Google Scholar 

  74. S. Obara, K. Kitaura and K. Morokuma, J. Am. Chem. Soc. 106, 7482 (1984)

    Article  CAS  Google Scholar 

  75. J.O. Noell and P.J. Hay, J. Am. Chem. Soc. 104, 4578 (1982)

    Article  CAS  Google Scholar 

  76. N. Koga and K. Morokuma, J. Phys. Chem. 94, 5454 (1990)

    Article  CAS  Google Scholar 

  77. T. Ziegler, V. Tschinke, L. Fan and A.D. Becke, J. Am. Chem. Soc. 111, 9177 (1989)

    Article  CAS  Google Scholar 

  78. R. Ahlrichs, P. Scharf and C. Erhardt, J. Chem. Phys. 82, 890 (1985)

    Article  CAS  Google Scholar 

  79. D.P. Chong and S.R. Langhoff, J. Chem. Phys. 84, 5606 (1986)

    Article  CAS  Google Scholar 

  80. GAUSSIAN 92, Revision A, M.J. Frisch, G.W. Trucks, M. Head-Gordon, P.M.W Gill, M.W. Wong, J.B. Foresman, B.G. Johnson, H.B. Schlegel, M.A. Robb, E.S. Replogle, R. Gomperts, J.L.Andres, K. Ragavachari, J.S. Binkley, C. Gonzales, R.L. Martin, D.J. Fox. D.J. Defrees, J. Baker, J.J.P. Stewart and J.A. Pople, Gaussian, Inc. (1992), Pittsburgh PA

    Google Scholar 

  81. P.J. Hay and W.R. Wadt, J. Chem. Phys. 82, 299 (1985)

    Article  CAS  Google Scholar 

  82. P.E.M. Siegbahn and M. Svensson, to be published

    Google Scholar 

  83. S.A. Mitchell, M.A. Blitz, P.E.M. Siegbahn and M. Svensson, J. Chem. Phys. 100,423 (1994)

    Article  CAS  Google Scholar 

  84. M.R.A. Blomberg, U.B. Brandemark, P.E.M. Siegbahn, J. Wennerberg and C.W. Bauschlicher, Jr., J. Am. Chem. Soc. 110, 6650 (1988)

    Article  CAS  Google Scholar 

  85. T. Lee, private communication

    Google Scholar 

  86. C.M. Rohlfìng and R.L. Martin, Chem. Phys. Lett. 115, 104 (1985)

    Article  Google Scholar 

  87. L.G.M. Pettersson and H. Ã…keby, J. Chem. Phys. 94, 2968 (1991)

    Article  CAS  Google Scholar 

  88. R.L. Martin, J. Phys. Chem. 87, 750 (1983).

    Article  CAS  Google Scholar 

  89. R.D. Cowan and D.C. Griffin, J. Opt. Soc. Am. 66, 1010(1976)

    Article  CAS  Google Scholar 

  90. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, to be published

    Google Scholar 

  91. C.W. Bauschlicher, Jr. and S.R.LanghofT, Chem. Phys. Lett. 177, 133 (1991)

    Article  CAS  Google Scholar 

  92. S.A. Mitchell, Ch.12 in Gas-Phase Metal Reactions, A. Fontijn, Ed., Elsevier (1992), Amsterdam

    Google Scholar 

  93. M.R.A. Blomberg, P.E.M. Siegbahn, U. Nagashima and J. Wennerberg, J. Am. Chem. Soc. 113,424(1991)

    Article  CAS  Google Scholar 

  94. J.W. Kauffman, R.H. Haugeand J.L. Margrave, J. Phys. Chem. 89, 3541 (1985)

    Article  CAS  Google Scholar 

  95. J.W. Kauffman, R.H. Hauge and J.L. Margrave, J. Phys. Chem. 89, 3547 (1985)

    Article  CAS  Google Scholar 

  96. L.S. Sunderlin and P.B. Armentrout, J. Am. Chem. Soc. 111, 3845 (1989)

    Article  CAS  Google Scholar 

  97. A.K. Rappé, C.J. Casewit, K.S. Colwell, W.A. Goddard III and W.M. Skiff, J. Am. Chem. Soc. 114, 10024(1992)

    Article  Google Scholar 

  98. P.E.M. Siegbahn and M.R.A. Blomberg, to be published

    Google Scholar 

  99. Crabtree, R.H. In Selective Hydrocarbon Activation: Principles and Progress, J.A. Davies, P.L. Watson, A., Greenberg and J.F. Liebman, Ed., VCH Publishers (1990), New York, pp. 1–18

    Google Scholar 

  100. M.R.A. Blomberg, P.E.M. Siegbahn and M. Svensson, to be published

    Google Scholar 

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  1. Department of Physics, University of Stockholm, Box 6730, S-113 85, Stockholm, Sweden

    P. E. M. Siegbahn & Margareta R. A. Blomberg

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  1. Van ’t Hoff Research Institute, University of Amsterdam, The Netherlands

    Piet W. N. M. Van Leeuwen

  2. C.L. Emerson Center, Emory University, Atlanta, USA

    Keiji Morokuma

  3. Theoretical Chemistry Group, University of Utrecht, The Netherlands

    Joop H. Van Lenthe

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Siegbahn, P.E.M., Blomberg, M.R.A. (1995). Oxidative Addition Reactions. In: Van Leeuwen, P.W.N.M., Morokuma, K., Van Lenthe, J.H. (eds) Theoretical Aspects of Homogeneous Catalysis. Catalysis by Metal Complexes, vol 18. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0475-3_2

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