| Title: |
Mechanochemical Synthesis, Characterization and Reactivity of a Room Temperature Stable Calcium Electride |
| Authors: |
Bowles AWJ; Quirk JA; Liu Y; Morritt GH; Freitag M; Whitehead GFS; Woodward AW; Brookfield A; Goodwin CAP; Collison D; Tuna F; McMullin CL; Dawson JA; Lu E; Ortu F |
| Source: |
Journal of the American Chemical Society, 2024 |
| Publisher Information: |
American Chemical Society |
| Publication Year: |
2024 |
| Collection: |
Newcastle University Library ePrints Service |
| Description: |
© 2024 The Authors. Published by American Chemical Society.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. |
| Document Type: |
article in journal/newspaper |
| File Description: |
application/pdf |
| Language: |
unknown |
| Relation: |
https://eprints.ncl.ac.uk/301750; https://eprints.ncl.ac.uk/fulltext.aspx?url=301750/639040C5-830E-4A30-AAF3-8438A40A5985.pdf&pub_id=301750 |
| Availability: |
https://eprints.ncl.ac.uk/301750 |
| Rights: |
https://creativecommons.org/licenses/by/4.0/ |
| Accession Number: |
edsbas.52A2B865 |
| Database: |
BASE |