Download e-book for kindle: Contemporary Problems in Carbonium Ion Chemistry I/II by Vladimir Alexandrovich Barkhash (auth.), Ch. Rees (eds.)

By Vladimir Alexandrovich Barkhash (auth.), Ch. Rees (eds.)

ISBN-10: 366215286X

ISBN-13: 9783662152867

ISBN-10: 3662152886

ISBN-13: 9783662152881

In 1965 a publication by way of P. Bartlett seemed less than the name "The Nonclassical Ions" 1). The publication is a suite of papers reprinted from quite a few journals. the numerous experiences that experience seemed because 2-22) are both antiquated (the e-book released in 1972 12) covers the literature mostly earlier than 1968) or fairly biased (e.g., 3.4,10ยป on short 2, 7,11). This evaluation makes an attempt to debate a number of the issues of view at the "nonclassical" carbocations. the most element is to set up the relative function of "nonclassical" and "classical" ions in a number of chemical procedures. the writer has P. Bartlett's suggestion 1) that once environment forth the achievements of the human brain one should still see how we got here to the trendy figuring out of a given challenge (" ... how we all know what we know"). the idea of "nonclassical" ions bargains an evidence of many precise chemical, stereochemical and kinetic peculiarities of bicyclic compounds. It has increased our wisdom on chemical bonds in carbocations by means of introducing electron-deficient bonds (as in boron hydrides). It has accounted for plenty of rearrangements of reliable cations. As a "side" outcome our wisdom has been prolonged approximately ionization procedures in an answer, in addition to approximately stereochemical tools. 2 major phrases of Nonclassical Carbocations In 1939 Hevell, Salas and Wilson 23) assumed an intermediate, "bridge" ion 2 to be shaped while camphene hydrochloride 1 is rearranged into isobornyl chloride three. This occurred 17 years after Meerwein first postulated the intermediate formation of "carbonium" ions in chemical reactions.

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Finally, the ab initio calculations made in 1971-72 by Pople and co-workers 129) clearly confirm the ions of type 5 to be more stable than those of type 71 since the former are homoaromatic, the latter are not; also most of the strain energy of the norbornane molecule is due to the distortion of normal angles. 803 A) C-C bonds in corner-protonated cyclopropane. Traylor's data make it possible to judge which groups can participate in stabilizing the cation entre by the "vertical" route. As for the correlation with solvolysis rates it may be (see Ref.

2 2 The theoretical calculation of the 34 (1+ values from the PMO theory was developed by Jorgensen 94,. Nonclassical Carbocations Thus, it is not the Q + value, but the "break" on the Hammett-Brown curve which testifies the changing mechanism and the onset of cr- or 1t-participation. This criterion, however, is of low sensitivity, it is only applicable to systems with very strong anchimeric assistance. oPNi ~OPNB Ar Ar Apparently all aryl groups, even the most electron-seeking, are 1t-donors and so they decrease the demand of the cation centre for the cr- and 1t-participation.

It is all the more impossible to deny - and the author himself admits it - that the acceleration of 2-exo-norbornyl tosylate solvolysis is due to both vertical and nonvertical processes. Hoffman's 130) theoretical investigations show that there is no contradiction between a-participation and hyperconjugation. The great variation in nuclear motion depends on the systems. 9 C Due to the skeleton rigidity in the 3-nortricyclyl cations the a-delocalization between the C-C bonds of the cyclopropane ring and the vacant p-orbital is highly restricted.

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Contemporary Problems in Carbonium Ion Chemistry I/II by Vladimir Alexandrovich Barkhash (auth.), Ch. Rees (eds.)


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