Direct observation of the wheland intermediate in electrophilic aromatic substitution. Reversible formation of nitrosoarenium cations

Journal of the American Chemical Society

Volumn 122, Issue 34, 2000, Pages 8279-8288

  Hubig, Stephan M ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATION; NAPHTHALENE DERIVATIVE; NITRIC OXIDE; NITROSO DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

ABSORPTION SPECTROSCOPY; ARTICLE; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; ELECTRON TRANSPORT; NITROSATION; TEMPERATURE DEPENDENCE;

EID: 0034734326     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja001318u     Document Type: Article

References (74)

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41. The preliminary assignment will be substantiated throughout this report by a thorough analysis of its spectroscopic and kinetic properties.
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45. -1 at 195 K. Extrapolation to [HMB] = 0 led to a lifetime of τ = 20 μs at 195 K.
46. -1 at T = 195 K, which is 30 times slower than that of HMB.
47. + EDA π-complex which is stable at low (-78 °C) temperatures.
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53. Dhanasekaran, T.; Kochi, J. K., unpublished results.
54. 13C NMR) and X-ray structures of various hexaalkylbenzenium ions, see: Hubig, S. M.; Kochi, J. K. J. Org. Chem., in press.
55. 4f,37b
56. (b) Dhanasekaran, T.; Lindeman, S. V.; Kochi, J. K., unpublished results.
57. CL) of nitrosoarenium from the radical pair.
58. Back-electron transfer in ion-radical pairs follows first-order kinetics since no diffusional processes are involved.
59. 38 we cannot discount a direct (one-step) alternative suggested by a reviewer involving the heterolytic cleavage of the NO-arene bond.
60. Rathore, R.; Lindeman, S. V.; Kochi, J. K. J. Am. Chem Soc. 1997, 119, 9393.
61. ET does not include any inner-sphere component to electron-transfer.
62. ET does not include any inner-sphere component to electron-transfer.
63. -1 approach those of barrier-free reactions. See ref 27, p 173.
64. 14,15
65. 41
66. 14
67. + EDA complexes. However, mere are conflicting results about the Wheland intermediate, viz., nitrosoarenium, which -depending on the method and level of the calculation - is obtained either as a more or less stable minimum or as a saddle point (transition state) between the EDA complex and N-protonated nitrosobenzene. Our experimental results reported here support the CISD/6-31G(d) calculations which predict a large energy barrier for the conversion of the σ-complex to an N-protonated nitrosobenzene and thus identify the deprotonation of the Wheland intermediate as the rate-determining step,
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