Although tunneling by carbon is much less common than tunneling by hydrogen, it can occur when the barrier to reaction is low and, even more important, narrow. Noradamantyl-Chloro-Carbene has been found experimentally to undergo ring expansion at cryogenic temperatures at a rate 10?111 times faster than the expected by classical transition state theory; this can only be attributed to heavy atom tunneling. We will discuss the calculations that reproduce this observation, and predict the �tunneling control� of other Noradamantyl-Carbene systems. In addition, the possibility of tunneling in the bond shifting of anti-aromatic compounds will be analyzed.

Heavy atom tunneling on carbene and anti-aromatic systems

247th National Meeting (2014)

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