Is there theoretical evidence for mutual influence between halogen and pnicogen-hydride bonds? An ab initio study

Abstract

Ab initio MP2 /6-311 ++G(d,p) level calculations have been carried out to investigate the interplay between the halogen and pnicogen-hydride bonds in NCX ⋯OPH 3⋯HMgY complexes (X = F, Cl, Br; Y = F, Cl, Br, H). The results indicated that the cooperative effects are obvious in the target complexes. These effects were considered in detail in terms of electrostatic potential, energetic, geometric, charge-transfer and electron density properties of the complexes. The values of cooperative energy (Ecoop) were ranging from −0.41 to −0.60 kJ /mol, −1.02 to −1.57 kJ /mol and −1.50 to −2.28 kJ /mol for X = F, Cl and Br, respectively. Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the triads are amplified with respect to the dyads. Mutual influence between the halogen and pnicogen-hydride bonds is investigated by ab initio calculations. Cooperative effects were observed in the dyad and triad complexes in which halogen and pnicogen-hydride bonds coexist.