Diverse World of Unconventional Hydrogen Bonds

This Account presents our view of unconventional intermolecular hydrogen bonds (HBs) for organometallic complexes and transition-metal or main-group hydrides. Over the past decade, low-temperature spectroscopic (IR, UV, and NMR) studies combined with theoretical calculations have disclosed the static and dynamic features of different HBs. Their guiding role in the proton-transfer processes was determined, as well as the energetic characteristics of HB intermediates and the activation barriers. Nevertheless, there is still much to explore in terms of the prediction of HB properties and control of protonation/deprotonation processes.