a greatly under-appreciated fundamental principle of physical organic chemistry很大程度上被忽视的基本原则物理有机化学.pdfVIP

Int. J. Mol. Sci. 2011, 12, 8316-8332; doi:10.3390/ijm OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 /journal/ijms Review A Greatly Under-Appreciated Fundamental Principle of Physical Organic Chemistry Robin A. Cox † Formerly Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON, M5S 3H6, Canada † Present address: 16 Guild Hall Drive, Scarborough, ON, M1R 3Z8, Canada; E-Mail: robin.a.cox@sympatico.ca; Tel.: +1-416-759-9625. Received: 19 October 2011; in revised form: 10 November 2011 / Accepted: 14 November 2011 / Published: 28 November 2011 Abstract: If a species does not have a finite lifetime in the reaction medium, it cannot be a mechanistic intermediate. This principle was first enunciated by Jencks, as the concept of an enforced mechanism. For instance, neither primary nor secondary carbocations have long enough lifetimes to exist in an aqueous medium, so SN 1 reactions involving these substrates are not possible, and an SN2 mechanism is enforced. Only tertiary carbocations and those stabilized by resonance (benzyl cations, acylium ions) are stable enough to be reaction intermediates. More importantly, it is now known that neither H3O+ nor HO– exist as such in dilute aqueous solution. Several recent high-level calculations on large proton clusters are unable to localize the positive charge; it is found to be simply “on the cl