Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H2O or NH3; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation
2023
Junjie Song | Mengyang Wang | Xiaocheng Xu | Qinghao Shao | Ying Zhao | Guiqiu Zhang | Nan Sun
Charge-shift (CS) bonding is a new bonding paradigm in the field of chemical bonds. Our recent study has revealed that certain Cu/Ag/Au-bonds display both CS bonding and &omega:-bonding characters. In this investigation, we extend our study to halogen bonding. Our focus is on scrutinizing the CS bonding in halogen-bonded BXY (B is a small Lewis base H2O or NH3: X and Y are halogen atoms) complexes by using natural bond orbital (NBO) analysis, natural resonance theory (NRT), and atoms in molecules (AIM) methods. The primary objective is to establish a connection between halogen bonding (B&ndash:X) in BXY and CS bonding in free XY (di-halogens). The calculations indicate that the studied BXY can be classified into two types. One type with a weak halogen bond shows closed-shell interaction. The other type with a stronger B&ndash:X interaction exhibits both CS bonding and &omega:-bonding characters (as seen in NH3ClF, NH3BrF, and NH3IF). Another interesting finding is a novel propensity that the CS bonding in free XY tends to carry over the halogen bonding in BXY, and the same propensity is found in Cu/Ag/Au &omega:-bonded species. The present study may offer an approach to probe CS bonding in many more 3c/4e &omega:-bonded molecules.
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