Quenching of n,π*-excited states in the gas phase: Variations in absolute reactivity and selectivity

Journal of the American Chemical Society

Volumn 124, Issue 38, 2002, Pages 11349-11357

  Klapstein, Dieter ^a   Pischel, Uwe ^b   Nau, Werner M ^b  

^a ST FRANCIS XAVIER UNIVERSITY   (Canada)

^b UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN TRANSFER;

AMINES; CATALYST SELECTIVITY; ELECTRONS; ETHERS; ISOTOPES; QUENCHING;

CHEMICAL ANALYSIS;

ARTICLE; CHEMICAL REACTION KINETICS; COMPETITIVE INHIBITION; GAS EXCHANGE; NONHUMAN; PHASE TRANSITION; PROTON TRANSPORT; SOLVATION; STEREOCHEMISTRY;

EID: 0037174415     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja020400h     Document Type: Article

References (58)

1. Scaiano, J. C. J. Photochem. 1973, 2, 81-118.
2. Wagner, P. J.; Truman, R. J.; Puchalski, A. E.; Wake, R. J. Am. Chem. Soc. 1986, 108, 7727-7738.
3. Hubig, S. M.; Rathore, R.; Kochi, J. K. J. Am. Chem. Soc. 1999, 121, 617-626.
4. Coenjarts, C.; Scaiano, J. C. J. Am. Chem. Soc. 2000, 122, 3635-3641.
5. Pischel, U.; Nau, W. M. J. Am. Chem. Soc. 2001, 123, 9727-9737.
6. Pischel, U.; Nau, W. M. J. Phys. Org. Chem. 2000, 13, 640-647.
7. Pischel, U.; Zhang, X.; Hellrung, B.; Haselbach, E.; Muller, P.-A.; Nau, W. M. J. Am. Chem. Soc. 2000, 122, 2027-2034.
8. Nau, W. M.; Pischel, U. Angew. Chem., Int. Ed. 1999, 38, 2885-2888.
9. Sinicropi, A.; Pischel, U.; Basosi, R.; Nau, W. M.; Olivucci, M. Angew. Chem., Int. Ed. 2000, 39, 4582-4586.
10. Pischel, U.; Allonas, X.; Nau, W. M. J. Inf. Rec. 2000, 25, 311-321.
11. Rebbert, R. E.; Ausloos, P. J. Am. Chem. Soc. 1965, 87, 5569-5572.
12. Abuin, E. B.; Encina, M. V.; Lissi, E. A.; Scaiano, J. C. J. Chem. Soc., Faraday Trans. 1 1975, 71, 1221-1229.
13. Berger, M.; Camp, R. N.; Demetrescu, I.; Giering, L.; Steel, C. Isr. J. Chem. 1977, 16, 311-317.
14. Lendvay, G.; Bérces, T. J. Photochem. Photobiol. A 1987, 40, 31-45.
15. Borisevich, N. A.; Karberuk, D. V.; Lysak, N. A.; Tolstorozhev, G. B. Zh. Prik. Spektrosk. 1989, 50, 745-749.
16. Matsushita, Y.; Kajii, Y.; Obi, K. J. Phys. Chem. 1992, 96, 4455-4458.
17. Matsushita, Y.; Yamaguchi, Y.; Hikida, T. Chem. Phys. 1996, 213, 413-419.
18. Zalesskaya, G. A.; Baranovskii, D. I.; Sambor, E. G. J. Appl. Spectrosc. 1999, 66, 76-80.
19. Nau, W. M.; Greiner, G.; Rau, H.; Wall, J.; Olivucci, M.; Scaiano, J. C. J. Phys. Chem. A 1999, 103, 1579-1584.
20. Solomon, B. S.; Thomas, T. F.; Steel, C. J. Am. Chem. Soc. 1968, 90, 2249-2258.
21. Askani, R. Chem. Ber. 1965, 98, 2551-2555.
22. Marquez, C.; Nau, W. M. Angew. Chem., Int. Ed. 2001, 40, 4387-4390.
23. Nau, W. M.; Greiner, G.; Wall, J.; Rau, H.; Olivucci, M.; Robb, M. A. Angew. Chem., Int. Ed. Engl. 1998, 37, 98-101.
24. Pischel, U.; Nau, W. M. Photochem. Photobiol. Sci. 2002, 1, 141-147.
25. Nau, W. M.; Cozens. F. L.; Scaiano, J. C. J. Am. Chem. Soc. 1996, 118, 2275-2282.
26. -1 was calculated from the sphere collision model (cf. Levine, I. N. Physical Chemistry; McGraw-Hill, Inc.: New York. 1995; p 442.). DBO (r = 3.07 Å. cf. ref 8) and diethylamine (r = 3.44 Å, calculated, this work) were used as representative reactants.
27. Nau, W. M.; Greiner, G.; Rau, H.; Olivucci, M.; Robb, M. A. Ber. Bunsen-Ges. Phys. Chem. 1998, 102, 486-492.
28. Sinicropi, A.; Pogni, R.; Basosi, R.; Robb, M. A.; Gramlich, G.; Nau, W. M.; Olivucci, M. Angew. Chem., Int. Ed. 2001, 40, 4185-4189.
29. Zimmerman, H. E.; Alabugin, I. V. J. Am. Chem. Soc. 2001, 123, 2265-2270.
30. Adam, W.; Moorthy, J, N.; Nau, W. M.; Scaiano, J. C. J. Org. Chem. 1997, 62, 8082-8090.
31. Nau, W. M. Ber. Bunsen Ges. Phys. Chem. 1998, 102, 476-485.
32. Nau, W. M. J. Am. Chem. Soc, 1998, 120, 12614-12618.
33. The antibonding derives from the fact that the energy of a three-center transition state (X···H···Y) for hydrogen abstraction is also dependent on the X-Y bond strength: N-N bonds are much weaker than C-N bonds, thereby causing decreased antibonding in the transition state, which accelerates the reaction, e.g., hydrogen abstraction from N-H relative to C-H. This effect has been discussed for photoinduced hydrogen abstraction reactions in ref 24 and is well established for hydrogen abstractions by radicals, cf, Zavitsas, A. A.; Chatgilialoglu, C. J. Am. Chem. Soc. 1995, 117, 10645-10654.
34. Note that a stereoelectronic effect for diisopropyl ether, which has been postulated in the reaction with t-butoxyl radicals (cf. Malatesta, V.; Scaiano, J. C. J. Org. Chem. 1982, 47, 1455-1459), was not observed in the present study.
35. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943.
36. Shtarev, A. B.; Tian, F.; Dolbier, W. R., Jr.; Smart, B. E. J. Am. Chem. Soc. 1999, 121, 7335-7341.
37. Laarhoven, L. J. J.; Mulder, P.; Wayner, D. D. M. Acc. Chem. Res. 1999, 32, 342-349.
38. Zavitsas, A. A.; Pinto, J. A. J. Am. Chem. Soc. 1972, 94, 7390-7396.
39. Encina, M. V.; Diaz, S.; Lissi, E. Int. J. Chem. Kinet. 1981, 13, 119-123.
40. Kirkwood, J. G. J. Chem. Phys. 1934, 2, 351-361.
41. Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486-1493.
42. Laurence, C.; Nicolet, P.; Dalati, M. T.; Abboud, J.-L. M.; Notario, R. J. Phys. Chem. 1994, 98, 5807-5816.
43. Evans, C.; Scaiano, J. C.; Ingold, K. U. J. Am. Chem. Soc. 1992, 114, 4589-4593.
44. Guttenplan, J. B.; Cohen, S. G. J. Org. Chem. 1973, 38, 2001-2007.
45. Inbar, S.; Linschitz, H.; Cohen, S. G. J. Am. Chem. Soc. 1982, 104, 1679-1682.
46. -1, cf. Turecek, F. J. Phys. Chem. 1994, 98, 3701-3706.
47. Wayner, D. D. M.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932.
48. Preliminary ab initio calculations at the CAS-SCF level of theory confirm a similar quenching mechanism for sulfides as for amines (ref 9), including the presence of an exciplex intermediate and a proximate conical intersection. Sinicropi, A.; Olivucci, M. Personal communication
49. Weast, R. C.; Lide, D. R.; Astle, M. J.; Beyer, W. H. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL, 1990.
50. Ivanov, M. G.; Zhuravlev, E. Z.; Dergunov, Y. I.; Elizarova, T. P. Zh. Obshch. Khim. 1990, 60, 1209-1212.
51. It should be kept in mind that the differences in the excitation energies in the gas phase and in solution, which are precisely known for DBO (Figure 1), are not accurately known for these triplet ketones (compare, for example, the results reported in Lin, Z.-P.; Aue. W. A. Spectrochim. Acta A 1999, 56, 111-117
52. with those in Cebul, F. A.; Kirk, K. A.; Lupo, D. W.; Pittenger, L. M.; Schuh, M. D.; Williams, I. R.; Winston, G. C. J. Am. Chem. Soc. 1980, 102. 5656-5661. This presents an uncertainty in the interpretation of the gas-phase reactivity of triplet ketones.
53. Yip, R. W.; Loutfy, R. O.; Chow, Y. L.; Magdzinski, L. K. Can. J. Chem. 1972, 50, 3426-3431.
54. -1) was observed (ref 13), which is in agreement with a full electron transfer.
55. Cumming J. B.; Kebarle, P. J. Am. Chem. Soc. 1977, 99, 5818-5820.
56. Lin, Z.-P.; Aue, W. A. Spectrochim. Acta A 1999, 56, 111-117.
57. Griller, D.; Howard, J. A.; Marriott, P. R.; Scaiano, J. C. J. Am. Chem. Soc. 1981, 103, 619-623.
58. Linstrom, P. J.; Mallard, W. G. NIST Chemistry WebBook; NIST Standard Reference Database No. 69; National Institute of Standards and Technology: Gaithersburg, MD, 2001.