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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 (in EN)

Journal Article · · Angewandte Chemie (International Edition)
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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

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