Mechanochemical Synthesis, Characterization and Reactivity of a Room Temperature Stable Calcium Electride

Alex Bowles, James Quirk, Yu Liu, George Morritt, Marina Freitag, George Whitehead, Adam Woodward, Adam Brookfield, Conrad Goodwin, David Collison, Floriana Tuna, Claire McMullin, James Dawson, Erli Lu, Fabrizio Ortu

Research output: Contribution to journalArticlepeer-review

Abstract

A new calcium-based Room temperature Stable Electride (RoSE), K[{Ca[N(Mes)(SiMe3)]3(e–)}2K3] (2), is successfully synthesized from the reaction of a calcium tris-amide, [Ca{N(Mes)(SiMe3)}3K] (1) (Mes = 2,4,6-trimethylphenyl), with potassium under mechanochemical treatment. The dimeric structure of K[{Ca[N(Mes)(SiMe3)]3(e–)}2K3] is calculated using ab initio random structure searching (AIRSS) methods. This shows the existence of highly localized anionic electrons (e–) and suggests poor electrical conductance, as confirmed via electroconductivity measurements. The two anionic electrons in 2 are strongly antiferromagnetically coupled, thus in agreement with the largely diamagnetic response from magnetometry. Reaction of 2 with pyridine affords 4,4′-bipyridine, while reaction with benzene gives C–H activation and formation of a calcium hydride complex, [K(η6-C6H6)4][{Ca[N(Mes)(SiMe3)](H)}2K3] (3). Computational DFT analysis reveals the crucial role played by the ligand framework in the stabilization of this new Ca-hydride complex.
Original languageEnglish
JournalJournal of the American Chemical Society
Early online date8 Oct 2024
DOIs
Publication statusPublished - 8 Oct 2024

Acknowledgements

For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence to the Author Accepted Manuscript version arising from this submission.

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