Charge-transfer mechanism for electrophilic aromatic nitration and nitrosation via the convergence of (ab initio) molecular-orbital and Marcus-Hush theories with experiments

Journal of the American Chemical Society

Volumn 125, Issue 11, 2003, Pages 3273-3283

  Gwaltney, Steven R ^a,b   Rosokha, Sergiy V ^a,b   Head Gordon, Martin ^a,b   Kochi, Jay K ^a,b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NITROSATION;

AROMATIC COMPOUNDS; COMPLEXATION; ELECTRON TRANSITIONS; OPTIMIZATION; POTENTIAL ENERGY; TOPOLOGY;

NITRATION;

NITRIC OXIDE; POLYCYCLIC AROMATIC HYDROCARBON;

AB INITIO CALCULATION; ARTICLE; CHEMICAL MODIFICATION; COMPLEX FORMATION; ELECTRON TRANSPORT; ENERGY; MOLECULAR INTERACTION; NITRATION; NITROSATION; SURFACE PROPERTY; THEORY;

EID: 0037454319     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021152s     Document Type: Article

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83. 0.5/2.
84. DA parameter in these strongly coupled systems.
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89. 70.]
90. 2• and
91. 2⇄, as described by Rosokha et al. in ref 37.
92. ET).
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95. -1.
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97. 36c (and the terms can be identified in their eq 3b). Typical values evaluated by this procedure for individual arene donors are: benzene (1.9 eV), toluene (2.5), p-xylene (2.6 eV) mesitylene (3.3 eV); but the evaluation of the better donors (approaching the isergonic region) suffers from the increasing inaccuracy of the denominator owing to: (1 - 2X) → 0.
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101. +) in ref 26.
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103. (a) Although there is extensive electron delocalization in both the precursor and successor complexes in eq 9, the charges are written inside (and not outside) the brackets to emphasize their individuality as separate PC and SC complexes.
104. + acceptor (LUMO) with 1.3e retaining the character of the arene HOMO.
105. 2•) which is conducive to bond formation and thus facilitates the formation of the σ-adduct in eq 11.
106. Although three other substantially higher-laying minima (probably accessed in the initial reactants encounter) were located, we expect their facile collapse to the stable π-complex owing to very low barriers and high exergonicities.
107. The transient structure in Figure 3A is from MP2/6-31G* calculations and will be further elaborated at the higher level of theory involving precise CCSD optimizations.
108. 54a does not materially affect this mechanistic formulation.
109. +) in Figure 7 must also be lowered by an extra amount described in footnote 63a.
110. (a) The charge-transfer formulation of aromatic nitrosation is thus best described as the combination of eq 5 plus eq 10.
111. ET represents the maximum (activation) barrier, provided reversibility is not included. However, some degree of the latter may have to be included to accommodate the observed deuterium kinetic isotope effects, because they are minimal in the preequilibrium steps in eq 5.
112. +•//NO•, see: Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 2000, 122, 8279.
113. 57 is not an intermediate, but lies close to the transition state in CCSD optimizations. Interestingly, the insertion in eq 10 is related to the organometallic process with carbonylmetal donors recently described by Melenkivitz, R.; Southern J. S.; Hillhouse G. L.; Concolino, T. E.; Liable-Sands, L. M.; Rheingold, A. L. J. Am.Chem. Soc. 2002, 124, 12 068.
114. 55.
115. (c) The nitrous-acid catalysis of aromatic nitration (and particularly the CIDNP results of Ridd et al.) have important bearing directly on this point (see the discussion by Olah et al. in ref 65, pp 129 ff.
116. 2•) state that leads to homolytic dissociation similar to the gas-phase behavior observed by:
117. (b) Schmitt, R. J.; Butrill, S., E. Jr.;: Ross, D. S. J. Am. Chem. Soc. 1984, 106, 626.
118. (c) Morrison, J. D.; Stenney, K.; Tedder, J. M. J. Chem. Soc. Perkin Trans. 2 1981, 967.
119. (d) Attina, M.; Cacace, F.; Yanez, M. J. Am. Chem. Soc. 1987, 109, 5092.
120. (e) Attina, M.; Cacace, F. Gazz. Chim. Ital. 1988, 118, 241.
121. For the precise bond distance/angle parameters of this and other structures in Figures 1-3 calculated via the coupled-cluster CCSD optimizations, see the coordinates listed in the Supplementary Information Available.
122. Hubig, S. M.; Kochi, J. K. J. Org. Chem. 2000, 65. 6807.
123. + moieties occurs in the PC → SC (Marcus-Hush) and the π → σ (molecular-orbital) transformations.
124. 2• radicals(compare footnotes 53 and 54).
125. 2•), see Figure 6 in Kim, E. K.; Bockman, M. T.; Kochi, J. K. J. Am. Chem. Soc. 1993, 115, 3103.
126. -1.
127. (a) The cationic sigma complex is an energy minimum in nitration whereas it is (or lies close to) the transition state for nitrosation.
128. 62 whereas such a smooth transformation cannot occur with nitrosation.
129. (c) For the quantitative comparison of the potential-energy diagram in Figure 8 with that applicable to aromatic nitration in solution, a minor energy adjustment for solvation (especially between the diabatic products state and the π- and σ-complexes) must be made, as described for aromatic nitrosation in footnote 52b.
130. For the least motion in electrophilic aromatic substitution, see: Rosokha, S. V.; Kochi, J. K. J. Org. Chem. 2002, 67, 1727.
131. 64.
132. 37.
133. 63d.
134. (d) Lee, K. Y.; Kuchynka, D. J.; Kochi, J. K. Inorg. Chem. 1990, 29, 4196.
135. 63a, c.
136. +] in Figure 8 as a comparison to aromatic nitration.
137. (c) We hope that further (theoretical) studies will more fully quantify the effects of the solvation on the potential-energy diagrams.
138. Olah, G. A., Malhotra, R., Narang, S. C. Nitration: Methods and Mechanisms; VCH: New York, 1989.
139. (a) The quotation is from Olah et al. in ref 65, p 166.
140. (b) Olah's requirement for and description of two (separate) intermediates in aromatic nitration are clearly presented on pp 134 ff.
141. For an early attempt, see: Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 2928.
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145. (d) For the recent update on aromatic donors, see: Rosokha S.; Kochi, J. K. In. Modern Arene Chemistry; Astruc, D., Ed.; VCH-Wiley: New York, 2002 (chapter 13), pp 435 ff.
146. DA, the potential-energy diagrams increasingly take on a more traditional character. with the high-energy σ-complex approaching the rate-limiting transition state.
147. 69c and this points to the occurrence of common intermediates.
148. (c) Kim, E. K.; Lee, K. Y.; Kochi, J. K. J. Am. Chem. Soc. 1992, 114, 1756.
149. 36b, c as illustrated in Figure S1 in Supporting Information.
150. Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1981, 103, 7240, and references therein.
151. Compare the gas-phase studies in ref 55b-d.