17O NMR spectroscopic characterization and the mechanism of formation of alkyl hydrotrioxides (ROOOH) and hydrogen trioxide (HOOOH) in the low- temperature ozonation of isopropyl alcohol and isopropyl methyl ether: Water- assisted decomposition

Chemistry - A European Journal

Volumn 6, Issue 5, 2000, Pages 809-819

  Plesničar, Božo ^a   Cerkovnik, Janez ^a   Tekavec, Tomaž ^a   Koller, Jože ^a  

^a UNIVERSITY OF LJUBLJANA   (Slovenia)

Author keywords

Ab initio calculations; Alky hydrotrioxides; Density functional calculations; Hydrogen trioxide; NMR spectroscopy

Indexed keywords

2 PROPANOL; OZONE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; DECOMPOSITION; DENSITY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLARIZATION;

EID: 0042996209     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(20000303)6:5<809::AID-CHEM809>3.0.CO;2-8     Document Type: Article

References (91)

1. For reviews, see: a) P. S. Bailey, Ozonation in Organic Chemistry, Vol. 2, Academic Press, New York, 1982, pp. 255-328; b) For a review on polyoxides, see: B. Plesničar in Organic Peroxides (Ed.: W. Ando), Wiley, Chichester, 1992, pp. 479-533; c) G. A. Olah, A. Molnar, Hydrocarbon Chemistry, Wiley, New York, 1995, pp. 291-312.
2. For reviews, see: a) P. S. Bailey, Ozonation in Organic Chemistry, Vol. 2, Academic Press, New York, 1982, pp. 255-328; b) For a review on polyoxides, see: B. Plesničar in Organic Peroxides (Ed.: W. Ando), Wiley, Chichester, 1992, pp. 479-533; c) G. A. Olah, A. Molnar, Hydrocarbon Chemistry, Wiley, New York, 1995, pp. 291-312.
3. For reviews, see: a) P. S. Bailey, Ozonation in Organic Chemistry, Vol. 2, Academic Press, New York, 1982, pp. 255-328; b) For a review on polyoxides, see: B. Plesničar in Organic Peroxides (Ed.: W. Ando), Wiley, Chichester, 1992, pp. 479-533; c) G. A. Olah, A. Molnar, Hydrocarbon Chemistry, Wiley, New York, 1995, pp. 291-312.
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13. For a preliminary account, see: B. Plesnicar, J. Cerkovnik, T. Tekavec, J. Koller, J. Am. Chem. Soc. 1998, 120, 8005, and the corresponding Supporting Information.
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15. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
16. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
17. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
18. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
19. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
20. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
21. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
22. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
23. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
24. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
25. For previous experimental and theoretical studies on HOOOH, see: a) P. A. Giguere, K. Herman, Can. J. Chem. 1970, 48, 3473; b) B. H. J. Bielski, H. A. Schwartz, J. Phys. Chem. 1968, 72, 3836; c) D. Cremer, J. Chem. Phys. 1978, 69, 4456; d) B. Plesničar, J. Cerkovnik, J. Koller, F. Kovac, J. Am. Chem. Soc. 1991, 113, 4946; e) C. F. Jackels, J. Chem. Phys. 1993, 99, 5768; f) J. Cerkovnik, B. Plesničar, J. Am. Chem. Soc. 1993, 115, 12169; g) J. Koller, B. Plesničar, J. Am. Chem. Soc. 1996, 118, 2470; h) S. L. Khursan, V. V. Shereshovets, Russ, Chem. Bull. 1996, 45, 1312; i) M. Speranza, Inorg. Chem. 1996, 35, 6140; j) T. Fujii, M. Yashiro, H. Tokiwa, J. Am. Chem. Soc. 1997, 119, 12280; k) D. J. Mckay, J. S. Wright, J. Am. Chem. Soc. 1998, 120, 1003.
26. 2) and water.
27. 1H NMR spectra of the ozonized solutions of 1b. (F. E. Stary, D. E. Emge, R. W. Murray, J. Am. Chem. Soc. 1976, 98, 1880.)
28. a) E. B. Wilson, Z. Smith, Acc. Chem. Res. 1987, 20, 257;
29. b) The intramolecularly hydrogen-bonded form of 2a, MP2/6-31 ++ G* (B3LYP/6-31G*): -418.69163 au (-419.85283). The "open" form of 2a: -418.68858 au (-419.84948).
30. J. Koller, M. Hodošček, B. Plesničar, J. Am. Chem. Soc. 1990, 112, 2124.
31. 17O NMR of HOOH, see: G. A. Olah, A. L. Berrier, G. K. S. Prakash, J. Am. Chem. Soc. 1982, 104, 2373.
32. L. Olsson, D. Cremer, J. Phys. Chem. 1996, 100, 1681.
33. S. Scheiner, M. Cuma, J. Am. Chem. Soc. 1996, 118, 1511.
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35. 3, -224.85979 au);
36. b) R. Wrobel, W. Sander, E. Kraka, D. Cremer, J. Phys. Chem. A 1999, 103, 3693, and references cited therein.
37. D. H. Giamalva, D. F. Church, W. A. Pryor, J. Am. Chem. Soc. 1986, 108, 7678.
38. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
39. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
40. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
41. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
42. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
43. +, see: a) R. J. Blint, M. D. Newton, J. Chem. Phys. 1973, 59, 6220; b) K. B. Mathisen, P. E. M. Siegbahn, J. Chem. Phys. 1984, 90, 225; c) M. Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer, J. Chem. Phys. 1986, 84, 2691; d) M. A. Vincent, I. H. Hillier, J. Phys. Chem. 1995, 99, 3109; e) T. P. W. Jungkamp, J. H. Seinfeld, Chem. Phys. Lett. 1996, 257, 15; f) A. J. C. Varandas, H. G. Yu, Mol. Phys. 1997, 91, 301.
44. ·, see Supporting Information.
45. It is also indicative that the geometry of TS1 resembles that of the forming 2-hydroxy-2-propyl radical (d(C-O) = 1.385 Å) more than that of 2-hydroxy-2-propyl cation (1.281 Å) (see Supporting Information).
46. For previous calculations on HOOO , see: a) K. B. Mathisen, O. Gropen, P. N. Skancke, U. Wahłgren, Acta Chem. Scand. A, 1983, 37, 817: b) see ref. [7g].
47. For previous calculations on HOOO , see: a) K. B. Mathisen, O. Gropen, P. N. Skancke, U. Wahłgren, Acta Chem. Scand. A, 1983, 37, 817: b) see ref. [7g].
48. 3OOO , see Supporting Information.
49. -1 at the B3LYP/6-31 ++ G* level of theory (see Supporting Information). The characteristic feature of this adduct was an even longer HO-OO "bond" and a somewhat shortened HOO-O bond relative to the non-solvated HOOO "anion". The mechanism of the fragmentation of this assembly is currently under investigation in our laboratory.
50. Our preliminary studies of the topology of the potential energy surface descending from the transition state TS1 by using IRC calculations (C. Gonzalez, H. B. Schlegel, J. Chem. Phys. 1989, 90, 2154; J. Phys. Chem. 1990, 94, 5523) have confirmed the intermolecularly hydrogen-bonded radical pair, that is, hydrotrioxyl radical 2-hydroxy-2-propyl radical complex (O-H ⋯ OOOH) as the first intermediate product. The IRC calculations of further reactions of this radical pair to form the end products of the title reaction (currently under invesitigation but computationally very time consuming) are beyond the scope of the present study. We thank one of the reviewers for suggesting these studies.
51. Our preliminary studies of the topology of the potential energy surface descending from the transition state TS1 by using IRC calculations (C. Gonzalez, H. B. Schlegel, J. Chem. Phys. 1989, 90, 2154; J. Phys. Chem. 1990, 94, 5523) have confirmed the intermolecularly hydrogen-bonded radical pair, that is, hydrotrioxyl radical 2-hydroxy-2-propyl radical complex (O-H ⋯ OOOH) as the first intermediate product. The IRC calculations of further reactions of this radical pair to form the end products of the title reaction (currently under invesitigation but computationally very time consuming) are beyond the scope of the present study. We thank one of the reviewers for suggesting these studies.
52. X.-M. Zhang, J. Org. Chem. 1998, 63, 1872.
53. a) M. Speranza, J. Phys. Chem. A 1998, 102, 7535;
54. b) for the first direct experimental evidence for HOOO radical, see: F. Cacace, G. de Petris, F. Pepi, A. Troiani, Science 1999, 285, 81.
55. 2, d(O-O) = 1.211 Å, E = -150.04486 au).
56. 2), and also reacts with isopropyl alcohol to form isopropoxymethanol.
57. 3)].
58. -1, logA = 7.8. (For a complete list of kinetic data, see Supporting Information.)
59. a) W. A. Pryor, N. Ohto, D. F. Church, J. Am. Chem. Soc. 1983, 105, 3614:
60. 6]acetone, :B, see Scheme 2) affects the outcome of the reaction.
61. CCSD(T)/6-311 ++ G**, HOOOH: d(H-O) = 0.978 Å, d(O-O) = 1.432 Å, ≮ H-O-O = 101.9 , ≮ O-O-O = 107.6 , ≮ H-O-O-O = 82.0 , E = -226.267699 au.
62. See also: C. von Sonntag, H.-P. Schuchmann, in Peroxyl Radicals (Ed.: Z. Alfassi), Wiley, New York, 1997, pp. 173-234.
63. All attempts to obtain anhydrous solutions of ROOOH/HOOOH with molecular sieves as drying agent (dry box) failed, since water was formed as a result of the induced decomposition of HOOOH by ozone as well as in the spontaneous decomposition of this polyoxide. Molar ratio HOOOH:HOH was in all cases approximately 1:2-3.
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77. [44d, 44e] for example, obtained at the B3LYP level, are remarkably close to those calculated at CCSD, CCSD(T), and QICD levels of theory.
78. a) P. Borowski, K. Andersson, P.-A. Malmqvist, B. O. Roos, J. Chem. Phys. 1992, 97, 5568;
79. b) F. Jensen, Introduction to Computational Chemistry, Wiley, 1999, p. 287;
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81. d) K. N. Houk, J. Liu, N. C. DeMello, K. R. Condroski, J. Am. Chem. Soc. 1997, 119, 10147;
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84. b) R. J. Bartlett, J. D. Watts, S. A. Kucharski, J. Noga, Chem. Phys. Lett. 1990, 165, 513 (CCSD(T)).
85. [7c, 7g, 7k, 11, 47b]
86. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.
87. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.
88. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.
89. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.
90. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.
91. See, for example: a) D. Cremer, J. Chem. Phys. 1978, 69, 4440; b) For a comprehensive discussion of the early use of ab initio methods (including MP calculations) for the study of peroxides and polyoxides, see: D. Cremer, in The Chemistry of Peroxides (Ed.: S. Patai), Wiley, Chichester, 1993, pp. 1-84; c) J. E. Carpenter, F. Weinhold, J. Phys. Chem. 1988, 92, 4306, and references cited therein; d) J. A. Dobado, J. M. Molina, J. Phys. Chem. 1993, 97, 7499; e) O. Mo, M. Yanez, I. Roxas, J. Elguero, J. Chem. Phys. 1994, 100, 2871; f) Y. -Y. Chuang, D. G. Truhlar, J. Phys. Chem. A 1999, 103, 651.