Noncovalent interactions in alkane chemistry

The selective functionalization of alkanes remains one of the mainstream objectives of modern synthetic chemistry, because these inert hydrocarbons derived from natural gas and oil are the most readily available (and inexpensive) natural carbon resources. Moreover, noncovalent interactions (hydrogen, halogen, chalcogen, pnicogen, tetrel, and icosagen bonds, as well as agostic, anagostic, π-π stacking, n-π*, π-cation and π-anion interactions, etc.) or their cooperation with coordination bonds can be employed for selective activation of covalent bonds in synthetic operations. According to the CCDC structural database, many cyclic and acyclic alkanes have been isolated as solid organic or inorganic associates, combined via noncovalent interactions. These interactions can be used in separation, transportation, or storage of alkanes and can weaken C-H or C-C bonds eventually toward their functionalization, issues that are discussed in this chapter. © 2019 John Wiley & Sons Ltd.