Synthesis and Crystal Structure of Anhydrous Di-iodyl Carbonate (IO 2 ) 2 [CO 3 ], Hosting I 5+ -Cations
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2025-10-14 |
| Journal | JACS Au |
| Authors | Dominik Spahr, Lkhamsuren Bayarjargal, Lukas BrĂźning, Valentin Kovalev, Elena Bykova |
| Institutions | European Synchrotron Radiation Facility, Dassault Systèmes (United Kingdom) |
| Citations | 1 |
Abstract
Section titled âAbstractâThe anhydrous di-iodyl carbonate (IO<sub>2</sub>)<sub>2</sub>[CO<sub>3</sub>] has been synthesized in a laser-heated diamond anvil cell at 30(2) GPa and 1600(200) K by a reaction of I<sub>2</sub>O<sub>5</sub> with CO<sub>2</sub>. Its monoclinic crystal structure (<i>C</i>2/<i>c</i> with <i>Z</i> = 4) was determined from synchrotron single crystal X-ray diffraction data. The experimental structural model was confirmed by density functional theory based calculations in combination with experimental Raman spectroscopy. (IO<sub>2</sub>)<sub>2</sub>[CO<sub>3</sub>]-<i>C</i>2/<i>c</i> belongs to the family of sp<sup>2</sup>-carbonates, and its crystal structure is characterized by the presence of nearly trigonal-planar [CO<sub>3</sub>]<sup>2-</sup> groups. In contrast to other iodide-containing carbonates, in this structure the iodine atoms are present as small and highly oxidized I<sup>5+</sup>-cations and not as large I<sup>-</sup>-anions. The I<sup>5+</sup>-cations are coordinated by seven oxygen atoms. The successful synthesis of (IO<sub>2</sub>)<sub>2</sub>[CO<sub>3</sub>]-<i>C</i>2/<i>c</i> represents a significant enlargement of the crystal chemistry of carbonates, as this chemically simple carbonate demonstrates that anhydrous carbonates with highly charged cations can be formed and that sp<sup>2</sup>-carbonates hosting a positively charged halogen atom as the only cation can be synthesized.