Calculations predict that carbon tunneling allows the degenerate cope rearrangement of semibullvalene to occur rapidly at cryogenic temperatures.
Calculations on the role of tunneling in the degenerate Cope rearrangements of semibullvalene (1) and barbaralane (3) predict that, at temperatures below 40 K, tunneling from the lowest vibrational level should make the temperature-independent rate constants k = 1.43 x 10(-3) s(-1) and k = 7.28 x 10(-9) s(-1), respectively. An experiment, using semibullvalene-2(4)-d(1), is proposed to test the prediction of rapid tunneling by 1 at cryogenic temperatures.
Zhang
Xue
X
Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle #305070, Denton, Texas 76203-5017, USA.
Hrovat
David A
DA
Borden
Weston Thatcher
WT