Noble-Gas Hydrides: New Chemistry at Low Temperatures

Abstract

Noble-gas chemistry has been undergoing a renaissance in recent years, due in large part to noble-gas hydrides, HNgY, where Ng = noble-gas atom and Y = electronegative fragment. These molecules are exceptional because of their relatively weak bonding and large dipole moments, which lead to strongly enhanced effects of the environment, complexation, and reactions. In this Account, we discuss the matrix-isolation synthesis of noble-gas hydrides, their spectroscopic and structural properties, and their stabilities.This family of species was discovered in 1995 and now has 23 members that are prepared in noble-gas matrices (HXeBr, HKrCl, HXeH, HXeOH, HXeO, etc.). The preparations of the first neutral argon molecule, HArF, and halogen-free organic noble-gas molecules (HXeCCH, HXeCC, HKrCCH, etc.) are important highlights of the field. These molecules are formed by the neutral H + Ng + Y channel. The first addition reaction involving HNgY molecules was HXeCC + Xe + H --> HXeCCXeH, and this led to the first hydride with two noble-gas atoms (recently extended by HXeOXeH). The experimental synthesis of HNgY molecules starts with production of H and Y fragments in solid noble gas via the UV photolysis of suitable precursors. The HNgY molecules mainly form upon thermal mobilization of the fragments.One of the unusual properties of these molecules is the hindered rotation of some HNgY molecules in solid matrices; this has been theoretically modeled. HNgY molecules also have unusual solvation effects, and the H-Xe stretching mode shifts to higher frequencies (up to about 150 cm-1) upon interaction with other species.The noble hydrides have a new bonding motif: HNgY molecules can be represented in the form (H-Ng)+Y-, where (H-Ng)+ is mainly covalent, whereas the interaction between (HNg)+ and Y- is predominantly ionic. The HNgY molecules are highly metastable species representing high-energy materials. The decomposition process HNgY --> Ng + HY is always strongly exoergic; however, the decomposition is prevented by high barriers, for instance, about 2 eV for HXeCCH. The other decomposition channel HNgY --> H + Ng + Y is endothermic for all prepared molecules.Areas that appear promising for further study include the extension of argon chemistry, preparation of new bonds with noble-gas atoms (such as Xe-Si bond), and studies of radon compounds. The calculations suggest the existence of related polymers, aggregates, and even HNgY crystals, and their experimental preparation is a major challenge. Another interesting task, still in its early stages, is the preparation of HNgY molecules in the gas phase.