Stabilization Of The CN ₃ ⁵⁻ Anion In Recoverable High‐pressure Ln ₃ O ₂ (CN ₃ ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates

Journal Article · Mon Oct 16 00:00:00 UTC 2023 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202311516 · OSTI ID:2580571

Aslandukov, Andrey ; Jurzick, Pascal ; Bykov, Maxim ; Aslandukova, Alena ; Chanyshev, Artem ; Laniel, Dominique ; Yin, Yuqing ; Akbar, Fariia ; Khandarkhaeva, Saiana ; Fedotenko, Timofey ; Glazyrin, Konstantin ; Chariton, Stella ; Prakapenka, Vitali ; Wilhelm, Fabrice ; Rogalev, Andrei ; Comboni, Davide ; Hanfland, Michael ; Dubrovinskaia, Natalia ; Dubrovinsky, Leonid

Abstract A series of isostructural Ln₃O₂(CN₃) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high‐pressure (25–54 GPa) high‐temperature (2000–3000 K) conditions in laser‐heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single‐crystal X‐ray diffraction (SCXRD) as well as corroborated by X‐ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln₃O₂(CN₃) solids are composed of the hitherto unknown CN₃⁵⁻guanidinate anion—deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln₃O₂(CN₃) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln₃O₂(CN₃) compounds are recoverable to ambient conditions. The stabilization of the CN₃⁵⁻guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: USDOE
• Grant/Contract Number: AC02-06CH11357
• OSTI ID: 2580571
• Journal Information: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 47 Vol. 62; ISSN 1433-7851
• Publisher: WileyCopyright Statement
• Country of Publication: United States
• Language: EN