Ethylene epoxidation with tungsten diperoxo complexes: Is relativity the origin of reactivity?

Journal of Physical Chemistry A

Volumn 105, Issue 19, 2001, Pages 4765-4772

  Deubel, Dirk V ^a  

^a UNIVERSITY OF CALGARY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDATION;

ACTIVATION ENERGY; OXIDATION; PROBABILITY DENSITY FUNCTION; REACTION KINETICS; TUNGSTEN COMPOUNDS;

ETHYLENE;

EID: 0035901825     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0100497     Document Type: Article

References (121)

1. (a) Wittcoff, H. A.; Reuben, B. G. Industrial Organic Chemicals; Wiley: New York, 1996.
2. (b) Weissermel, K.; Arpe, H.-J. Industrial Organic Chemistry, 3rd ed.; Wiley-VCH: Weinheim, 1997.
3. (a) Mimoun, H.; Seree de Roch, I.; Sajus, L. Bull. Soc. Chem. Fr. 1969, 1481.
4. (b) Mimoun, H.; Seree de Roch, I.; Sajus, L. Tetrahedron 1970, 26, 37.
5. (c) Mimoun, H. Angew. Chem. 1982, 94, 750;
6. Angew. Chem., Int. Ed. Engl. 1982, 21, 734.
7. 3)] is only one of the active species. For instance, protonated diperoxo species, which might exist in the catalytic system in small concentrations, are more reactive than the parent complex (ref 8d).
8. Wahl, G.; Kleinhenz, D.; Schorm, A.; Sundermeyer, J.; Stowasser, R.; Rummey, C.; Bringmann, G.; Fickert, C.; Kiefer, W. Chem. Eur. J. 1999, 5, 3237.
9. (a) Schulz, M.; Teles, J. H.; Sundermeyer, J.; Wahl, G. (BASF AG) DE 195.33.331.4, 1995.
10. (b) Schulz, M.; Teles, J. H.; Sundermeyer, J.; Wahl, G. (BASF AG) WO 10054, 1995.
11. Wu, Y. D.; Sun, J. J. Org. Chem. 1998, 63, 1752.
12. (a) Gisdakis, P.; Antonczak, S.; Köstlmeier, S.; Herrmann, W. A.; Rösch, N. Angew. Chem. 1998, 110, 2333;
13. Angew. Chem., Int. Ed. Engl. 1998, 37, 2211.
14. (b) Kühn, F. E.; Santos, A. M.; Roesky, P. W.; Herdtweck, E.; Scherer, S.; Gisdakis, P.; Yudanov, I. V.; Di Valentin, C.; Rösch, N. Chem. Eur. J. 1999, 5, 3603.
15. (c) Di Valentin, C.; Gisdakis, P.; Yudanov, I. V.; Rösch, N. J. Org. Chem. 2000, 65, 2996.
16. (d) Yudanov, I. V.; Di Valentin, C.; Gisdakis, P.; Rösch, N. J. Mol. Catal. 2000, 158, 189.
17. (e) Di Valentin, C.; Gandolfi, R.; Gisdakis, P.; Rösch, N. J. Am. Chem. Soc. 2001, 123, 2365.
18. (a) Deubel, D. V.; Sundermeyer, J.; Frenking, G. Inorg. Chem. 2000, 39, 2314.
19. (b) Deubel, D. V.; Sundermeyer, J.; Frenking, G. J. Am. Chem. Soc. 2000, 122, 10101.
20. (c) Deubel, D. V.; Frenking, G.; Senn, H. M.; Sundermeyer, J. Chem. Commun. 2000, 2469.
21. (d) Deubel, D. V.; Sundermeyer, J.; Frenking, G. Org. Lett. 2001, 3, 329.
22. (e) Deubel, D. V.; Sundermeyer, J.; Frenking, G. Eur. J. Inorg. Chem. 2001, 100427, in press.
23. Jørgensen, K. A.; Hoffmann, R. Acta Chem. Scand. B 1986, 40, 411.
24. (a) Purcell, K. F. J. Organomet. Chem. 1983, 252, 181.
25. (b) Purcell, K. F. Organometallics 1985, 4, 509.
26. Ti-catalyzed olefin epoxidation has also theoretically been studied; for example, see: (a) Wu, Y. D.; Lai, D. K. W. J. Am. Chem. Soc. 1995, 117, 11327.
27. (b) Wu, Y. D.; Lai, D. K. W. J. Org. Chem. 1995, 60, 673.
28. (c) Karlsen, E.; Schoffel, K. Catal. Today 1996, 32, 107.
29. (d) Tantanak, D.; Vincent, M. A.; Hillier, I. H. Chem. Commun. 1998, 1031.
30. (e) Sinclair, P. E., Carlow, C. R. A. J. Phys. Chem. B 1999, 103, 1084.
31. (f) Yudanov, I. V.; Gisdakis, P.; Di Valentin, C.; Rösch, N. Eur. J. Inorg. Chem. 1999, 2135.
32. Sundermeyer, J. Angew. Chem. 1993, 105, 1195;
33. Angew. Chem., Int. Ed. Engl. 1993, 32, 1144.
34. Sharpless, K. B.; Townsend, J. M.; Williams, D. R. J. Am. Chem. Soc. 1972, 94, 295.
35. N2 reactions, (ii) pericyclic reactions, for instance Diels-Alder reactions, and (iii) reactions with a coarctate TS topology such as olefin epoxidation with peroxy acids (ref 15) or dioxiranes (ref 16). Reactions of the latter class proceed by breaking and making two bonds at one or more atoms at a time. For details, see: (a) Herges, R. Angew. Chem. 1994, 106, 261.
36. (b) Herges, R. J. Chem. Inf. Comput. Sci. 1994, 34, 91. (Chemical Equation Presented) linear cyclic coarctate
37. (a) Plesnicar, B.; Tasevski, M.; Azman, A. J. Am. Chem. Soc. 1978, 100, 743.
38. (b) Bach, R. D.; Owensby, A. L.; Gonzalez C.; Schlegel, H. B. J. Am. Chem. Soc. 1991, 113, 2338.
39. (c) Yamabe, S.; Kondou C.; Minato, T. J. Org. Chem. 1996, 61, 616.
40. (d) Singleton, D. A.; Merrigan, S. R.; Liu, J.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 3385.
41. (e) Bach, R. D.; Canepa, C.; Winter, J. E.; Blanchette, P. E. J. Org. Chem. 1997, 62, 5191.
42. (f) Bach, R. D.; Glukhovtsev, M. N.; Gonzalez, C.; Marquez, M.; Estevez, C. M.; Baboul, A. G.; Schlegel, H. B. J. Phys. Chem. 1997, 101, 6092.
43. (g) Bach, R. D.; Estévez, C. M.; Winter, J. E.; Glukhovtsev, M. N. J. Am. Chem. Soc. 1998, 120, 680.
44. (h) Bach, R. D.; Glukhovtsev, M. N.; Canepa, C. J. Am. Chem. Soc. 1998, 120, 775.
45. (i) Bach, R. D.; Glukhovtsev, M. N.; Gonzalez, C. J. Am. Chem. Soc. 1998, 120, 9902.
46. (j) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, A. J. Org. Chem. 1999, 64, 3853.
47. (k) Marchand, A. P.; Ganguly, B.; Shukla, R.; Krishnudu, K.; Kumar, V. S.; Watson, W. H.; Bodige, S. G. Tetrahedron 1999, 55, 8313.
48. (l) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M. Tetrahedron 1999, 55, 11309.
49. (m) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, A. J. Org. Chem. 2000, 65, 2030.
50. (n) Chekroun, A.; Jarid, A.; Benharref, A.; Boutalib, A. J. Org. Chem. 2000, 65, 4431.
51. (o) Adam, W.; Bach, R. D.; Dmitrenko, O.; Saha-Möller, C. R. J. Org. Chem. 2000, 65, 6715.
52. (p) Gisdakis, P.; Rösch, N. Eur. J. Org. Chem. 2001, 719.
53. (q) Deubel, D. V. J. Org. Chem. 2001, 66, JO010127M, accepted.
54. (a) Bach, R. D.; Owensby, A. L.; Andres, J. L.; Schlegel, H. B. J. Am. Chem. Soc. 1991, 113, 7031.
55. (b) Bach, R. D.; Andres, J. L.; Owensby, A. L.; Schlegel, H. B.; McDouall, J. J. W. J. Am. Chem. Soc. 1992, 114, 7207.
56. (c) Houk, K. N.; Liu, J.; DeMello, N. C.; Condroski, K. R. J. Am. Chem. Soc. 1997, 119, 10147.
57. (d) Jenson, C.; Liu, J.; Houk, K. N.; Jørgensen, W. L. J. Am. Chem. Soc. 1997, 119, 12982.
58. (e) Miaskiewicz, K.; Smith, D. A. J. Am. Chem. Soc. 1998, 120, 1872.
59. (f) Liu, J.; Houk, K. N.; Dinoi, A.; Fusco, C.; Curci, R. J. Org. Chem. 1998, 63, 8565.
60. (g) Baboul, A. G.; Schlegel, H. B.; Glukhovtsev, M. N.; Bach, R. D. J. Comput. Chem. 1998, 12, 1353.
61. (h) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, A. Tetrahedron 1998, 54, 12323.
62. (i) Selcuki, C.; Aviyente, V. J. Mol. Structure (THEOCHEM) 1999, 492, 165.
63. (j) Armstrong, A.; Washington, I.; Houk, K. N. J. Am. Chem. Soc. 2000, 122, 6297.
64. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
65. (a) Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
66. (b) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1558.
67. (c) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1755.
68. For recent examples, see: (a) Fonseca Guerra, C.; Bickelhaupt, F. M.; Snijders, J. G.; Baerends, E. J. J. Am. Chem. Soc. 2000, 122, 4117.
69. (b) Diefenbach, A.; Bickelhaupt, F. M.; Frenking, G. J. Am. Chem. Soc. 2000, 122, 6449.
70. (c) Uddin, J.; Frenking, G. J. Am. Chem. Soc. 2001, 123, 1683.
71. Becke, A. D. Phys. Rev. A 1988, 38, 3098.
72. Perdew, J. P. Phys. Rev. B 1986, 33, 8822.
73. Snijders, J. G.; Baerends, E. J.; Vernooijs, P. At. Data Nucl. Tables 1982, 26, 483.
74. Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
75. Krijn, J. G.; Baerends, E. J. Fit Functions in the HFS-Method; Internal Report (in Dutch); Vrije Universiteit Amsterdam: The Netherlands, 1984.
76. Deubel, D. V.; Schlecht, S.; Frenking, G. J. Am. Chem. Soc. 2001, 123, JA003733, under revision.
77. (a) Fonseca Guerra, C.; Snijders, J. G.; Te Felde, G.; Baerends, E. J. Theor. Chem. Acc. 1988, 99, 391.
78. (b) Bickelhaupt, F. M.; Baerends, E. J. Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 2000; Vol. 15, p 1.
79. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
80. Frenking, G.; Antes, I.; Böhme, M.; Dapprich, S.; Ehlers, A. W.; Jonas, V.; Neuhaus, A.; Otto, M.; Stegmann, R.; Veldkamp, A.; Vyboishchikov, S. F. Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; Vol. 8, p 63.
81. Deubel, D. V.; Frenking, G. J. Am. Chem. Soc. 1999, 121, 2021.
82. (a) Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939.
83. (b) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
84. Ehlers, A. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 111.
85. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294.
86. Fukui, K. Acc. Chem. Res. 1981, 14, 363.
87. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
88. (a) Pitzer, K. S. Acc. Chem. Res. 1979, 12, 271.
89. (b) Pyykkö, P.; Desclaux, J. P. Acc. Chem. Res. 1979, 12, 279.
90. (c) Christiansen, P. A.; Ermler, W. C.; Pitzer, K. S. Annu. Rev. Phys. Chem. 1985, 36, 407.
91. (d) Pyykkö, P. Chem. Rev. 1988, 88, 563.
92. (e) Almlöf, J.; Gropen, O. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; Vol. 8, p 203.
93. (f) Balasubramanian, K. Relativistic Effects in Chemistry; Wiley: New York, 1997.
94. (g) Schwerdtfeger P. Relativistic Effects in Chemistry; Lecture, University of Marburg, Germany, 1998.
95. Dirac, P. A. M. Proc. R. Soc. London 1928, 117, 610.
96. We have chosen a definition of the Dirac equation with (Matrix Presented) instead of (Matrix Presented) to align the nonrelativistic and relativistic energy scales.
97. (a) Snijders, J. G.; Baerends, E. J. Mol. Phys. 1979, 36, 1789.
98. (b) Snijders, J. G.; Baerends, E. J.; Ros, P. Mol. Phys. 1979, 38, 1909.
99. (a) Chang, C.; Pelissier, M.; Durand, P. Phys. Scr. 1986, 34, 394.
100. (b) Heully, J.-L.; Lindgren, I.; Lindroth, E.; Lundquist, S.; Martensson-Pendrill, A. M. J. Phys. B 1986, 19, 2799.
101. (c) Van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, 4597.
102. (d) Van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1994, 101, 9783.
103. (e) Van Lenthe, E.; Snijders, J. G.; Baerends, E. J. J. Chem. Phys. 1996, 105, 6505.
104. (f) Van Lenthe, E.; Van Leeuwen, R.; Baerends, E. J.; Snijders, J. G. Int. J. Quantum Chem. 1996, 57, 281.
105. (g) Van Lenthe, E.; Ehlers, A. E.; Baerends, E. J. J. Chem. Phys. 1999, 110, 8943.
106. (a) Bersuker, I. B.; Budnikov, S. S.; Leizerov, B. A. Int. J. Quantum Chem. 1972, 6, 849.
107. (b) Cowan, R. D.; Griffin, D. C. J. Opt. Soc. Am. 1976, 66, 1010.
108. (c) Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050.
109. The transition states show a significant anomeric effect, which was pointed out in our previous studies (ref 8ab). In the TS, the phosphorus-oxygen bond (P-O6) has a synperiplanar orientation to the active metalladioxirane moiety (M, O2, O3; see Figure 1) because the lone pair of O6 with an antiperiplanar orientation to the active metalladioxirane moiety supports the cleavage of the Mo-O3 bond.
110. There is no experimental activation energy available because the kinetic data presented in the pioneering work (ref 2b) were interpreted in favor of the wrong mechanism. BP86 activation barriers for the epoxidation of olefins with organic peracids (ref 15) are several kcal/mol lower than B3LYP values, which in turn underestimate experimental activation energies. In the present work, we employ the BP86 functional because both the fragment-based energy-decomposition scheme and BP86 are implemented in the ADF package while the hybrid functional is not.
111. (a) Bell, R. P. Proc. R. Soc. London, Ser. A 1936, 154, 414.
112. (b) Evans, M. G.; Polanyi, M. J. Chem. Soc., Faraday Trans. 1936, 32, 1340.
113. Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334.
114. The relation among the extent of reaction, the extent of asymmetry, and the electronic character at the TS for the epoxidation of various α olefins with peroxyformic acid and dioxirane was recently studied and the effects on reactivity were pointed out; for details, see ref 15q.
115. The attack of the σ*-(O-O) Orbital of electrophilic oxidants was postulated by Edwards: (a) Edwards, J. O. In Peroxide Reaction Mechanisms; Edwards, J. O., Ed.; Interscience: New York, 1962; p. 67.
116. (b) Curci, R.; Edwards, J. O. In Catalytic Oxidations with Hydrogen Peroxide as Oxidant; Strukul, G., Ed.; Kluwer: Dordrecht, 1992; p. 45.
117. The geometries of TS- and TS+ were calculated by adding -0.1 and 0.1, respectively, of the eigenvector that corresponds to the negative eigenvalue of the force-constants matrix to the coordinates of the stationary point.
118. (a) Ziegler, T.; Snijders, J. G.; Baerends, E. J. Chem. Phys. Lett. 1980, 75, 1.
119. (b) Snijders, J. G.; Pyykkö, P. Chem. Phys. Lett. 1980, 75, 5.
120. (c) Pyykkö, P.; Snijders, J. G.; Baerends, E. J. Chem. Phys. Lett. 1981, 83, 432.
121. (d) Ziegler, T.; Snijders, J. G.; Baerends, E. J. J. Chem. Phys. 1981, 74, 1271.