Theoretical Insights into Bifurcated Intramolecular Dihydrogen Bonds

Abstract

AbstractTwo‐ring intramolecular π‐electron delocalization assisted dihydrogen bonds existing in (1Z,4Z)‐1,4‐dipentene‐3‐bora‐1,5‐diol and its symmetrically substituted derivatives have been analysed here since the MP2/6‐311++G(d,p) calculations on these systems were performed. The influence of the coexistence of two intramolecular dihydrogen bonded rings in these molecular structures on properties of intramolecular dihydrogen bonds as well as on the π‐electron delocalization within these rings was investigated. The comparison with corresponding structures of typical two‐ring, so‐called resonance‐assisted, RAHB, systems was performed. The results of calculations show that such rings′ coexistence leads to the weakening of dihydrogen bonds, similarly as for the typical two‐ring RAHB systems. The Quantum Theory of ‘‘Atoms in Molecules’’ (QTAIM) was also applied here to get more details about the nature of dihydrogen bonds. Correlations between dihydrogen bond strength measures and other energetic, geometrical and topological parameters were also analysed. It was found that characteristics of bond critical points as well as of ring critical points are useful to estimate the strength of intramolecular dihydrogen bonds in two‐ring dihydrogen bonded systems discussed here. The Natural Bond Orbital, NBO, approach parameters are also discussed as useful ones to describe properties of dihydrogen bonded systems.