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Xenon Expands Its Molecular Portfolio

Noble-Gas Chemistry: Researchers report new additions to the collection of ‘inert gas’ compounds

by Stephen K. Ritter
October 19, 2015 | A version of this story appeared in Volume 93, Issue 41

The noble gases, which occupy the last column of the periodic table, were once thought to be inert and not capable of forming molecules. It has now been more than 50 years since that thinking has been debunked, and in that time an array of noble-gas compounds have been reported. Even so, when new versions are announced they are still considered noteworthy. In the latest examples, Gary J. Schrobilgen and his group at McMaster University, in Ontario, have reported two new types of xenon molecules. In one case, the researchers ran a reaction of XeF2 with ReO3F in anhydrous HF to prepare the bridging complex [XeOXeOXe][μ-F(ReO2F3)2]2. The cation is an unprecedented example of a xenon(II) oxide and noble-gas oxocation, as well as a rare example of a noble-gas dication (J. Am. Chem. Soc. 2015, DOI: 10.1021/jacs.5b08765). In a second case, the researchers treated the potent oxidant XeF6 with acetonitrile in a chlorofluorocarbon solvent to make the shock-sensitive compounds F6XeNCCH3 and F6Xe(NCCH3)CH3CN. These are the first examples of molecules with Xe(VI)–N bonds (Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201507635). With X-ray crystal structures and computational analysis, the researchers provide additional insight into xenon’s electronic structure and bonding abilities.

Credit: J. Am. Chem. Soc.
Crystal structure of [XeOXeOXe][μ-F(ReO2F3)2]2; Xe = purple, Re = lavender, F = green, O = red.
Credit: J. Am. Chem. Soc.
Credit: Angew. Chem. Int. Ed.
Crystal structure of F6XeNCCH3; Xe = purple, F = green, N = blue, C = gray, H = white.
Credit: Angew. Chem. Int. Ed.


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