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

Lookup NU author(s): Dr James Quirk, Harvey Morritt, Professor Marina FreitagORCiD, Dr James DawsonORCiD

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

© 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.

Publication metadata

Author(s): 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

Publication type: Article

Publication status: Published

Journal: Journal of the American Chemical Society

Year: 2024

Volume: 146

Issue: 42

Pages: 28914–28924

Print publication date: 23/10/2024

Online publication date: 08/10/2024

Acceptance date: 24/09/2024

Date deposited: 23/10/2024

ISSN (print): 0002-7863

ISSN (electronic): 1520-5126

Publisher: American Chemical Society

URL: https://doi.org/10.1021/jacs.4c09408

DOI: 10.1021/jacs.4c09408

Data Access Statement: Supporting information is available alongside the publication on the publisher’s page.

PubMed id: 39377174

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