Abstract

Part I
Quantum mechanical tunneling of “heavy” atoms (i.e. carbon) was recently proven to be extremely atypical, but also exceptionally rich chemistry, especially at cryogenic conditions. The only requirements are a rather low activation energy and, much more important, a narrow barrier. Through the theoretical analysis of the quantum tunneling driven reactions of carbenes and some degenerate rearrangements we will evaluate the novel concepts of isotopic controlled selectivity, tunneling stability and tunneling in antiaromatic systems.
 
Part II
Since the beginning of the 20th century, halogen bonds have shown to be a ubiquitous non-covalent interaction, appearing in biochemistry, crystal structures, and recently in catalysis. Since then a “gold rush” for finding more and more interactions of the same kind has brought a plethora of new terms: chalcogen bonds, tetrel bonds, aerogen bonds, s holes, p holes, etc. We will briefly explore through molecular orbital theory the origin of these interactions, while trying to make some sense in the confusions that plague them.