Metal-Catalysed Reactions of Hydrocarbons / 06-Exchange of Alkanes with Deuterium

opinion. The mechanisms suggested by Frennet for single and multiple exchange of methane and ethane differ radically from those originated by Kemball, and which form the basis of all the discussion concerning the behaviour of cycloalkanes, but unfortunately the effect of operating conditions on rates and multiplicities can be explained at least qualitatively by both. The safest conclusions to reach concerning mechanisms of cycloalkane exchange are that either (i) all reactions involve intermediates that are somewhere between the di-σ and π forms or (ii) that some molecules prefer to adopt a form more like one extreme, while others prefer another. Perhaps alkane exchange is like politics—the art of the possible.

The reader wishing to be informed of the intensity of the debate on these reaction mechanisms as it was exercised in the mid-1960s should read the relevant part of the discussion in Discussions of the Faraday Society, Vol. 42 (1966).

REFERENCES

1.A. Frennet, Catal. Rev. 10 (1974) 37.

2.C. Kemball, Adv. Catal. 11 (1959) 223.

3.L. Guczi, B.S. Gudkov and P. T´et´enyi, J. Catal. 24 (1972) 187.

4.G.C. Bond, Catalysis by Metals, Academic Press: London (1962).

5.D.W. McKee and F.J. Norton, J. Catal. 4 (1965) 510.

6.A. Frennet, A. Crucq, L. Degols and G. Lienard, Acta Chim. Hung. 111 (1982) 499; J. Catal. 53 (1978) 159.

7.L. Guczi, A. S´ark´any and P. T´et´enyi, Z. Phys. Chem. NF 74 (1971) 26.

8.J.R. Anderson and C. Kemball, Proc. Roy. Soc. A 226 (1954) 472; J.R. Anderson and B.G. Baker in: Chemisorption and Reactions on Metal Films, (J.R. Anderson, ed.), Academic Press: London, Vol. 2 (1971), p. 64.

9.G.C. Bond, Appl. Catal. A 149 (1997) 3.

10.J.R. Anderson and R.J. Macdonald, J. Catal. 13 (1969) 345.

11.J.A. Dalman and C. Mirodatos, J. Molec. Catal. 25 (1984) 161.

12.D.W. McKee, J. Phys. Chem. 70 (1966) 525.

13.A. Frennet, G. Lienard, A. Crucq and L. Degols, J. Catal. 53 (1978) 150.

14.F.G. Gault, Adv. Catal. 30 (1981) 1.

15.A. Frennet in: Hydrogen Effects in Catalysis, (Z. Pa´al and P.G. Menon, eds.), Dekker: New York (1988), p. 399.

16.G.A. Martin, Bull. Soc. Chim. Belg. 105 (1996) 131.

17.A. S´ark´any, K. Matusek and P. T´et´enyi, J. Chem. Soc. Faraday Trans. I 73 (1977) 1699.

18.L. Guczi, A. S´ark´any and P. T´et´enyi, J. Chem. Soc. Faraday Trans. I . 70 (1974) 1971.

19.L. Guczi and Z. Karpinski,´ J. Catal. 56 (1979) 438.

20.A. S´ark´any, L. Guczi and P. T´et´enyi, Acta Chim. Acad. Sci. Hung. 96 (1978) 27.

21.N. Khodakov, N. Barbouth, Y. Berthier, J. Oudar and P. Schulze, J. Chem Soc. Faraday Trans. 91 (1995) 569.

22.D.W. McKee, Trans. Faraday Soc. 61 (1965) 2273.

23.D.W. McKee and F.J. Norton, J. Catal. 56 (1964) 252.

24.G.C. Bond and E.G. Allison, Catal. Rev. 7 (1973) 25.

25.A. da Costa Faro Jr. and C. Kemball, J. Chem. Soc. Faraday Trans. 91 (1995) 741.

26.R. Brown and C. Kemball, J. Chem. Soc. Faraday Trans. 89 (1989) 2159.

27.G.A. Martin, J.A. Dalmon and C. Mirodatos, Bull. Soc. Chim. Belg. 88 (1979) 559.

28.I.H.B. Haining, C. Kemball and D.A. Whan, J. Chem. Res. (S), (1982) 296.

29.D. Garden, C. Kemball and D.A. Whan, J. Chem. Soc. Faraday Trans. I 82 (1986) 3113.

30.J.K.A. Clarke and J.F. Taylor, J. Chem. Soc. Faraday Trans. I 72 (1976) 917.

31.J.L. Vlasveld and V. Ponec, J. Catal, 44 (1976) 352.

32.F. Zaera, Proc. 10thInternat. Congr. Catal. (L. Guczi, F. Solymosi and P. T´et´enyi, eds.), Akad´emiai Kiado:´ Budapest B (1993), 1591.

33.A. Frennet and C. Hubert, J. Molec. Catal. A: Chem. 163 (2000) 163.

34.A. Frennet, Catal. Today 12 (1992) 131.

35.F. Zaera, Catal. Lett. 11 (1991) 95.

36.F. Zaera, Chem. Rev. 95 (1995) 2651.

37.K. Otsuka, S. Kobayashi and S. Takenaka, J. Catal. 200 (2001) 4.

38.J.R. Anderson and C. Kemball, Proc. Roy. Soc. A 223 (1954) 361.

39.P. T´et´enyi, L. Guczi and A. S´ark´any, Acta Chim. Acad. Sci. Hung. 97 (1978) 221; L. Guczi and A. S´ark´any, J. Catal. 68 (1981) 190.

40.A. Loaiza, Mingde Xu and F. Zaera, J.Catal. 159 (1996) 127.

41.F. Zaera and G.A. Somorjai, J. Phys. Chem. 89 (1985) 3211.

42.B.F. Hegarty and J.J. Rooney, J. Chem. Soc. Faraday Trans. I 85 (1989) 1861.

43.A. S´ark´any, L. Guczi and P. T´et´enyi, J. Catal. 39 (1976) 345.

44.R. Brown, C. Kemball, J.A. Oliver and I.H. Sadler, J. Chem. Res. (S) (1985) 274.

45.G.C. Bond and J. Addy, Trans. Faraday Soc. 53 (1957) 383, 388.

46.L. Guczi. B.S. Gudkov and P. T´et´enyi, J. Catal. 24 (1972) 187.

¨

47. H. Oz and T. Gaumann, J. Catal. 126 (1990) 115.

48. S.M. Davis and G.A. Somorjai, J. Phys. Chem 87 (1983) 1545. 49. F.G. Gault and C. Kemball, Trans. Faraday Soc. 57 (1961) 1781.

50. R.L. Burwell Jr. and R.H. Tuxworth, J. Phys. Chem. 60 (1956) 1043. 51. E.F. Meyer and C. Kemball, J. Catal. 4 (1965) 711.

52. R.L. Burwell Jr., B.K.C. Shim and H.C. Rowlinson, J. Am. Chem. Soc. 79 (1957) 5142. 53. T. Chevreau and F. Gault, J. Catal. 50 (1977) 124.

54. L. Guczi, A. S´ark´any and P. T´et´enyi, Bulg. Acad. Sci. (Comm. Dept. Chem.) 6 (1973) 349. 55. R. Burch and Z. Pa´al, Appl. Catal. A : Gen. 114 (1994) 9.

56. A.C. Faro Jr. and C. Kemball, J. Chem. Soc. Faraday Trans. I 82 (1986) 3125. 57. R. Brown and C. Kemball, J. Chem. Soc. Faraday Trans. 86 (1990) 435.

58. R. Brown, C. Kemball and I.H. Sadler, Proc. 9th Internat. Congr. Catal. (M.J. Phillips and M. Ternan, eds.), Chem. Inst. Canada: Ottawa 3 (1988) 1013.

59. R.L. Burwell Jr., Langmuir 2 (1986) 2. 60. R.L. Burwell Jr., Catal. Rev. 7 (1973) 25.

61. R. Brown and C. Kemball, J. Chem. Soc. Faraday Trans. 92 (1996) 281. 62. R. Brown, C. Kemball and I.H. Sadler, Proc. Roy. Soc. A 424 (1989) 39. 63. Z. Karpinski,´ J. Catal. 77 (1982) 118.

64. E. Eskinazi and R.L. Burwell Jr. J. Catal. 79 (1983) 118.

65. E.H. van Broekhoven and V. Ponec, J. Molec. Catal. 25 (1984) 109. 66. J.K.A. Clarke and J.J. Rooney, Adv. Catal. 25 (1976) 125.

67. Z. Karpinski´ and J.K.A. Clarke, J. Chem. Soc. Faraday Trans. I 75 (1975) 2063. 68. V. Ponec and W.M.H. Sachtler, J. Catal. 24 (1972) 250.

69. Y. Inoue, J.M. Herrmann, H. Schmidt, R.L. Burwell Jr., J.B. Butt and J.B. Cohen, J. Catal. 53 (1978) 401.

70. S.M. Augustine and W.M.H. Sachtler, J. Phys. Chem. 91 (1987) 5953. 71. J. Barbier, A. Morales and R. Maurel, Nouv. J. Chim. 4 (1980) 223. 72. R.L. Burwell Jr. and K. Schrage, Discuss. Faraday Soc. 41 (1966) 215.

73.R.L. Burwell Jr., Chem. Eng. News 44 (1966) 56.

74.R. Brown, A.S. Dolan, C. Kemball and G.S. McDougall, J. Chem. Soc. Faraday Trans. 88 (1992) 2045.

75.A. Roberti, V. Ponec and W.M.H. Sachtler, J. Catal. 28 (1973) 381.

76.J.J. Rooney, F.G. Gault and C. Kemball, Proc. Chem. Soc. (1960) 407.

77.J. Barbier, A. Morales, P. Mar´ecot and R. Maurel, Bull. Soc. Chim. Belg. 88 (1979) 569.

78.F.G. Gault and J.J. Rooney, J. Chem. Soc. Faraday Trans. I 75 (1979) 1320.

79.R.L. Burwell Jr. and K. Schrage, J. Am. Chem. Soc. 87 (1965) 5253.

80.J.J. Phillipson and R.L. Burwell Jr., J. Am. Chem. Soc. 92 (1970) 6125.

81.A. S´ark´any, L. Guczi and P. T´et´enyi, J. Catal. 39 (1975) 181.

82.L. Guczi and P. T´et´enyi, Acta Chim. Acad. Sci. Hung. 77 (1973) 417.

83.S.M. Augustine and W.M.H. Sachtler, J. Catal. 106 (1987) 417.

84.J.B. Butt, Appl. Catal. 15 (1985) 161.

85.G. Fitzsimmons, C. Hardacre, W.R. Patterson, J.J. Rooney, J.K.A. Clarke, M.R. Smith and R.M. Ormerod, Catal. Lett. 45 (1997) 187.

86.T. Baird, E.J. Kelly, W.R. Patterson and J.J. Rooney, J. Chem. Soc. Chem. Comm. (1992) 1431.

87.D. Lomot and Z. Karpinski,´ Catal. Lett. 60 (2000) 133.

88.Buchang Shi and B.H. Davis, J. Catal. 147 (1994) 38.