Bell, Nicola, Gladkikh, Marina, Fraser, Cameron, Elsayed, Mostafa, Richards, Emma  ORCID: https://orcid.org/0000-0001-6691-2377 and Drummond Turnbull, Richard
2025.
A cobotic, digitally‐controlled Schlenk‐line unlocks access to elusive Lewis‐base stabilised copper bis(disilylamides).
Angewandte Chemie
10.1002/ange.202505408
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Abstract
Silylamides are important ligands in coordination chemistry for their ability to stabilize low‐coordination numbers and provide soluble, and even volatile, metal complexes. Such compounds provide valuable insights into the fundamental bonding and reactivity of their respective metals. Despite the wealth of homo‐ and heteroleptic hexamethyldisilazide complexes of divalent 3d ions (Sc‐Ni, Zn), attempts to access the corresponding divalent copper complexes have, to date, yielded only Cu(I) species. Herein, we demonstrate the stabilization and isolation of a Cu(II) bis‐hexamethyldisilazide which was achieved by the implementation of digital chemistry tools. In order to successfully isolate (DMAP)CuII(N{SiMe3}2)2 (DMAP = N,N‐dimethylaminopyridine) we investigated the roles of the co‐ligand and silylamide transfer reagent in the kinetics of its formation. Crucial to these studies was our newly‐developed ‘Cobotic’ Schlenk‐line which allows for digital control of the atmosphere under which we conduct our highly reactive syntheses. In digitizing Schlenk‐line handling, we have improved synthetic productivity by creating protocols for automated inertization, solvent evaporation, liquid handling and crystallization all while capturing reaction log data. Importantly our Cu silylamide synthesis provides a case study showing that our cobotics approach allows for the discovery and isolation of unstable species which may remain elusive by traditional manual or fully autonomous methodologies.
| Item Type: | Article |
|---|---|
| Date Type: | Published Online |
| Status: | In Press |
| Schools: | Schools > Chemistry |
| Additional Information: | License information from Publisher: LICENSE 1: URL: http://onlinelibrary.wiley.com/termsAndConditions#vor, Start Date: 2025-06-03 |
| Publisher: | Wiley |
| ISSN: | 0044-8249 |
| Date of First Compliant Deposit: | 18 June 2025 |
| Date of Acceptance: | 3 June 2025 |
| Last Modified: | 18 Jun 2025 13:22 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/179095 |
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