Naslov
A new rearrangement process in tert-amyl cation

Autori
Vrček, Valerije ; Saunders, Martin ; Kronja, Olga

Izvornik
Journal of the American Chemical Society (0002-7863) 126 (2004), 42; 13703-13707

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
carbocation rearrangement; NMR spectroscopy; quantum chemical calculations

Sažetak
13C NMR spectroscopy of the 2-methyl-2-butyl-1-13 C cation ( 13 C-labeled tert-amyl cation) indicates that interchange of the inside and outside carbons occurs via a barrier of 19.5 ( 2.0 kcal/mol. A plausible mechanism involves hydride migration in the proposed 2-pentyl cation 4 to form 3-pentyl cation 5. Via the protonated cyclopropane intermediate 6, which undergoes degenerate corner-to-corner hydride shift, the secondary 3-pentyl cation with the label shifted to the central carbon atom is formed. The tert-amyl cation obtained from it in the reverse process has the 13C label on an inside carbon atom. All intermediates and transition structures were located on the PES theoretically at the MP2/6-31G(d, p) level of theory. The rearrangement rate of the doubly labeled tert-amyl cation (methyl-13 C-butyl-1-13 C cation), followed by means of 13 C NMR, revealed that the process that interchanges inside and outside carbons has the highest barrier. Comparison of the initial rates revealed that isotopomer 1e arises considerably more slowly than other isotopomers, indicating that in the overall rearrangement process transition structure 5-TS has the highest energy.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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