Noble Gas Binding Ability of an Au(I) Cation Stabilized by a Frustrated Lewis Pair: A DFT Study

Abstract

The noble gas (Ng) binding ability of a monocationic [(FLP)Au] + species has been investigated by a computational study. Here, the monocationic [(FLP)Au] + species is formed by coordination of Au(I) cation with the phosphorous (Lewis base) and the boron (Lewis acid) centers of a frustrated Lewis pair (FLP). The bonds involving Au and P, and Au and B atoms in [(FLP)Au] + are partially covalent in nature as revealed by Wiberg bond index (WBI) values, electron density analysis and energy decomposition analysis (EDA). The zero point energy corrected bond dissociation energy (D 0), enthalpy and free energy changes are computed for the dissociation of Au-Ng bonds to assess the Ng binding ability of [(FLP)Au] + species. The D 0 ranges from 6.0 to 13.3 kcal/mol, which increases from Ar to Rn. Moreover, the dissociation of Au-Ng bonds is endothermic as well as endergonic for Ng = Kr-Rn, whereas the same for Ng = Ar is endothermic but exergonic at room temperature. The partial covalent character of the bonds between Au and Ng atoms is demonstrated by their WBI values and electron density analysis. The Ng atoms get slight positive charges of 0.11-0.23 |e|, which indicates some amount of charge transfer takes place from it. EDA demonstrates that electrostatic and orbital interactions have equal contributions to stabilize the Ng-Au bonds in the [(FLP)AuNg] + complex.

Noble gas dative bonding with coinage metal carbene complexes: A theoretical study

“…The experimental and theoretical advances in complexes containing NgAu bonds were recently presented in a brief overview 42 . In 2020, a theoretical investigation was performed to study the interaction of a monocationic [(FLP)Au] + species with the noble gas (Ng) 43 . There are, however, numerous further theoretical investigations on Noble gas‐Noble metal bond 44–47 …”

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

“…The domain of the noble gas chemistry has expanded after the discovery of the first stable molecule of argon (HArF) characterized using the infrared absorption spectroscopic technique supported by ab initio quantum chemical calculations by Räsänen and co-workers in 2000. , Following this revolutionized work, various noble gas-containing neutral and charged chemical compounds − ,− have been predicted theoretically and prepared via suitable experimental techniques. In general, these metastable compounds are obtained by inserting a noble gas atom into a stable molecule having either astronomical significance such as HCO + , HCS + , and HN 2 + or environmental importance such as HOX (X = F, Cl, and Br) and H 3 O + .…”