Unveiling the Inverse Sandwich Complexes of XeO₃: A Computational Exploration

Our study introduces the design of inverse sandwich (iSw) complexes incorporating a noble gas compound: xenon trioxide (XeO₃). Through comprehensive computational analyses, we have investigated the critical factors influencing their stability by employing a variety of state-of-the-art computational tools. We demonstrated that the coordination number of xenon in the iSw complex of XeO₃ with 18-crown-6 is influenced by the presence of a rare, weakly stabilizing Xe···Xe interaction between the XeO₃ molecules. Furthermore, we observed that the stability of iSw complexes of 1,3,5-triphenylbenzene (TPB) and its derivatives is not solely attributed to aerogen bonding, but also involves contributions from C-H···O interactions and back-donation from the lone pair of Xe to the antibonding C-C orbitals of TPB. Additionally, the significant contributions from orbital interactions and dispersion interactions in the TPB derivatives highlight the multifaceted amphoteric properties of XeO₃ and reveal that the iSw complexes of TPB and derivatives are not predominantly governed by electrostatic interactions, contrary to conventional belief.