Structure and fluxional behavior of pentamethoxycarbonylcyclopentadiene View Full Text


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Article Info

DATE

2017-10

AUTHORS

G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev, V. I. Minkin

ABSTRACT

Quantum-chemical calculations by the density functional theory method at the B3LYP/6- 311++G** level have shown that the fulvene form of pentamethoxycarbonylcyclopentadiene 1 in the gas phase is more favorable in energy than cyclopentadiene form 2 by ΔEZPE = 7.8 kcal/mol. The fluxional behavior of fulvene 1, detected by dynamic NMR can be explained by the mechanism of circular low-barrier 1,9-O,O'-H shifts accompanied by rotations of the hydroxymethoxymethylene substituent about the С=С bond with the activation barrier ΔEZPE= 23.5 (gas) and 20.9 (CH2Cl2) kcal/mol. This reaction path is 18.6 kcal/mol more favorable in energy than transition of fulvene 1 to cyclopentadiene 2 with subsequent 1,5- sigmatropic hydrogen shifts in the five-membered ring. More... »

PAGES

230-234

Identifiers

URI

http://scigraph.springernature.com/pub.10.1134/s0012500817100020

DOI

http://dx.doi.org/10.1134/s0012500817100020

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1092448581


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