Origins of Nonperfect Synchronization in the Lowest-Energy Path of Identity Proton Transfer Reactions Leading to Delocalized Anions: A VBSCF Study 1 Nathan Harris, ‡,§ Wu Wei, ‡,| William H. Saunders, Jr.,* ,⊥ and Sason Shaik* ,‡ Contribution from the Department of Organic Chemistry and the Lise Meitner-MinerVa Center for Computational Quantum Chemistry, The Hebrew UniVersity, Jerusalem, 91904 Israel, Department of Chemistry, The State Key Laboratory for Physical Chemistry of Solid Surfaces and Institute of Physical Chemistry, Xiamen UniVersity, Xiamen 361005, P. R. China, and Department of Chemistry, UniVersity of Rochester, Rochester, New York 14627 ReceiVed March 23, 2000 Abstract: Two proton-transfer reactions yielding delocalized conjugate bases, the identity reactions of allyl anion with propene (2a) and acetaldehyde enolate with acetaldehyde (2b), are examined by means of quantum- chemical calculations and compared with another proton-transfer yielding a localized anion, methide ion with methane (9). When both reactants and transition structures are constrained to conformations that prevent delocalization, barriers are lower, showing that delocalization stabilizes the anions more than the transition structures. Calculations utilizing valence bond self-consistent field (VBSCF) methods show that in all three cases the single most important contributing structure to the hybrid is a triple ion species R - H + R - . This mixes well with localized covalent structures R-HR - and R - H-R, but poorly with delocalized covalent or triple ion structures. It is concluded that nonperfect synchronization in 2a and 2b results from a balance between maximizing resonance stabilization and maximizing covalent carbon-hydrogen bonding in the (R- - -H- - - R) - transition structure. We wish to report direct computational evidence that the lag in delocalization at the transition state in proton transfers from carbon acids yielding delocalized anions results from a balance between maximizing resonance stabilization and maximizing covalent bonding in the transition structure. It does not, contrary to a common assumption, deprive the transition structure of resonance stabilization that might otherwise lower the barrier. The first systematic discussion of the lag in delocalization that occurs in deprotonation of carbon acids such as nitro- methane was by Kresge. 2 The evidence he sought to explain was that the equilibrium acidity of nitroalkanes increases in the order nitromethane < nitroethane < 2-nitropropane, but the rate of proton abstraction decreases in the same order. This suggests that negative charge remains largely localized on the R-carbon atom in the transition structure but is relayed out to the oxygens in the product anions. He argued that the lag in delocalization of the negative charge arose because rehybridization in the transition structure was incomplete and thus only a fraction of the charge transferred from base to substrate could be delocal- ized within the developing conjugate base. This argument has been extended and quantified by Bernasconi as the Principle of Nonperfect Synchronization (PNS). 3 While the principle pro- vides a rigorous way of describing the phenomenon, it has never been clear why the reaction should choose this energy path when the fully synchronous and presumably lower-energy path seemed in principle to be available. If more delocalization and hence more stabilization could be gained by more complete rehybrid- ization in the transition state, why is rehybridization as limited as it is? Unease on this point is apparent in the statement “This state of affairs seems to contradict a basic law of nature, according to which physical or chemical processes should always follow a path of minimum energy”. 4 Clearly neither Bernasconi nor anyone else seriously believes that the PNS violates a basic law of nature, but why it should even appear to has remained a worrisome question. Qualitative paradigms that avoid this difficulty have been available for some time. Hine used the Principle of Least Nuclear Motion to argue that the geometric changes required in going from the reactant to the transition structure would increase the energy of a valence bond contributor with a reactant-like electron distribution and thus increase the barrier. 5 A crucial point was made by Pross and Shaik, who argued that an important contributor to the resonance hybrid transition structure in the deprotonation of nitromethane should be a triple ion species, 1, which would both lower the energy of the transition structure and lead to localization of charge on the carbon of the developing nitromethanate anion. 6 By this analysis ‡ The Hebrew University. § Present address 6509 Marsol Road, Apartment #620 Mayfield Heights, OH 44124. | Xiamen University. ⊥ University of Rochester, Rochester. (1) A preliminary account of part of this work was reported in J. Phys. Org. Chem. 1999, 12, 259-262. (2) (a)Kresge, A. J. Chem. Soc. ReV. 1973, 2, 475-503. (b) Kresge, A. J. Can. J. Chem. 1974, 52, 1897. (3) (a) Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301-308. (b) Bernasconi, C. F. Acc. Chem. Res. 1992, 25,9-16. (c) Bernasconi, C. F. AdV. Phys. Org. Chem. 1992, 27, 119-238. (d) Albery, W. J.; Bernasconi, C. F.; Kresge, A. J. J. Phys. Org. Chem. 1988, 1, 29-31. (4) Bernasconi, C. F.; Wenzel, P. J. J. Am. Chem. Soc. 1994, 116, 5405- 5413. (5) Hine, J. AdV. Phys. Org. Chem. 1977, 15, 1-61. B: - Η +- :CH 2 NO 2 1 6754 J. Am. Chem. Soc. 2000, 122, 6754-6758 10.1021/ja001032p CCC: $19.00 © 2000 American Chemical Society Published on Web 06/30/2000