Cs5([12]crown‐4)2(O3)5: A Supramolecular Compound Containing the Confined Ozonide Partial Structure ${{{\hfill 1\atop \hfill \infty }}}${Cs8(O3)10}2−

Nuss, Hanne; Jansen, Martin

doi:10.1002/anie.200603734

Cited by 6 publications

(3 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compared to the extensive investigations of the atomic oxygen ligand (oxo) and molecular O 2 ligands (superoxo and peroxo), − chemistry of the triatomic oxygen ligand (ozonide) is not well-developed. The stable ozonide compound is known only for the first and second elements. − It has been suggested that several solid surfaces generate the ozonide ion via the interaction with O 2 ; − however, the detailed geometric and electronic structures of the surface ozonide species have never been clarified due to the analytical difficulty of the solid surface. Too unstable metal ozonide species have been isolated only by applying the cryogenic matrix-isolation methods. − A breakthrough in an isolation approach for the stable metal ozonide species was reported in 2017 by Oda et al who demonstrated that the use of zeolite pores makes it possible to isolate and analyze the state of the metal ozonide species even under conditions closer to actual practical conditions, not just cryogenic temperatures. ,,, The first example of the stable single metal ozonide species is the [Zn II (O 3 –• )] + species that is stabilized as the counter cation for the negatively charged AlO 4 tetrahedra site.…”

Section: Introductionmentioning

confidence: 99%

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

et al. 2022

View full text Add to dashboard Cite

Molecular metal oxides are invoked as the key intermediate in a variety of oxidative reactions. Although an atomic oxygen ligand and molecular O 2 ligands are well known, the triatomic oxygen ligand (ozonide) is very limited due to its instability. Here, we report a successful preparation and characterization of stable cadmium ozonide species. Our approach used the negatively charged local environments within the zeolite pore, which allowed us to isolate the single cadmium ozonide species as the counter cation even at room temperature. Its state was characterized by vibronic progressions closely similar to those observed in the cryogenic inert-element matrix system. Density functional theory calculations determined the lowest-energy geometry as the side-on [Cd II (O 3 −• )] + having C 2v symmetry. This model was stable within the ab initio molecular dynamics simulation at 300 K, rationalizing the abnormal stability of [Cd II (O 3 −• )] + observed experimentally. The O 3 -a 1 → Cd-5s-donation orbital interaction was the driving force for the formation of the stable Cd II −(O 3 −• ) bond. The zeolite lattice plays a pivotal role in the enhancement of the acidity of the cadmium ion and stabilizes the donation interaction but constrains the O 3 adduct as a pseudo-free ozonide ion. The findings in the present work will be applicable for designing new metal ozonide compounds.

show abstract

Section: Introductionmentioning

confidence: 99%

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Mononuclear metal oxides are important intermediates in various oxidation reactions. − Bonding mechanisms of metal–oxygen are diverse, resulting in a variety of metal oxide structures with characteristic properties. So far, a considerable number of metal oxides in which a single atom of oxygen or molecular oxygen is bonded to a metal ion have been isolated and characterized crystallographically. − Well-established geometric and electronic states of the mononuclear metal oxides have further developed our understanding of the more complicated metal–oxygen oligomers including dimer and trimer. , On the other hand, the stable triatomic oxygen species bound to a metal ion, i.e., metal–ozonide, remains scarce due to the high reactivity of the ozonide ion; the crystallographic characterization is limited to the relatively stable ozonide complex of first and second group elements. − …”

Section: Introductionmentioning

confidence: 99%

¹⁷O-ESR Evidence for Zeolite Matrix Isolation of a Square Planar ZnO₃ Ring Radical with C_2v Symmetry

et al. 2021

View full text Add to dashboard Cite

Atomic-level insights into the geometric and electronic states of the metal–ozonide sequence remain scarce. We have recently found that a zeolite catalyst has a local environment to isolate the extremely rare mononuclear ZnII–ozonide species. In the present study, each atomic oxygen radical of the ZnII–ozonide species was selectively labeled with 17O, and each local environment was analyzed by electron spin resonance (ESR) spectroscopy at an X-band frequency, computer simulations of ESR spectra, density functional theory (DFT) calculations, and ab initio molecular dynamics (AIMD) simulations. The two types of 17O hyperfine structures assignable to the C 2v geometry of a square planar ZnO3 ring radical were obtained experimentally. The DFT calculations ascertained the ground-state C 2v geometry of the ZnII–ozonide adduct. This model provides 17O-hyperfine coupling constants that correspond well with the experimental parameters, supporting the generation of the C 2v ZnO3 ring radical. The C 2v ZnO3 ring radical is stable even at around room temperature, as evidenced by the similarity in the ESR spectra collected at 300 and 4 K. Such an unusual stability was supported by AIMD simulations, where C 2v geometry was preserved at least for 50 ps at 300 K. Molecular orbital analyses showed that the ozonide species is stabilized via the highly polarized ZnII–(O3 – ·) bonds. These interactions led to the polarization of two O–O bonds in the ozonide adduct, through which both side oxygens becomes anionic states, but the central oxygen becomes a cationic state. The zeolite lattice plays a pivotal role in constraining the effective charge of Zn close to (+2) and thereby stabilizing such a highly polarized ZnII–(O3 – ·) bond. These novel findings suggest that the zeolite lattice has the potential as the ligand to create reactive metal–oxygen radicals with an unprecedented shape and ionic states.

show abstract

“…There are numerous salts of [O 3 ] − , the so-called ozonide ion, such as with Cs + [33], its [12C4] [34] and [18C6] [35] crown ether complexes, and the tetramethyl "onium" salts [(CH 3 ) 4 N] + [33], [(CH 3 ) 4 P] + [36], and [(CH 3 ) 4 P] + [36]. Ozonides of small cations and/or polarizing ions such as Na + [37][38][39] and Ba 2+ [40] are comparatively unstable.…”

Section: -Oxygen Species (Species With Three Oxygens)mentioning

confidence: 99%

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

2020

View full text Add to dashboard Cite

In this review, we discuss different ions of oxygen and fluorine and related oxyfluorides and isoelectronic species from the viewpoint of their potential ambisaline character, defined as a property of species X so that both X + and X − may both be found in isolable salts. The term is applied to the ions as well as to the neutral precursor. Reactivity versus stability, reported and plausible synthetic approaches of well-established and probable species are discussed from the perspective of thermochemistry.

show abstract

Cs₅([12]crown‐4)₂(O₃)₅: A Supramolecular Compound Containing the Confined Ozonide Partial Structure ${{{\hfill 1\atop \hfill \infty }}}${Cs₈(O₃)₁₀}²⁻

Cited by 6 publications

References 34 publications

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

¹⁷O-ESR Evidence for Zeolite Matrix Isolation of a Square Planar ZnO₃ Ring Radical with C_2v Symmetry

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

Contact Info

Product

Resources

About

Cs5([12]crown‐4)2(O3)5: A Supramolecular Compound Containing the Confined Ozonide Partial Structure ${{{\hfill 1\atop \hfill \infty }}}${Cs8(O3)10}2−

Cited by 6 publications

References 34 publications

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

Identification of a Stable Ozonide Ion Bound to a Single Cadmium Site within the Zeolite Cavity

17O-ESR Evidence for Zeolite Matrix Isolation of a Square Planar ZnO3 Ring Radical with C2v Symmetry

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

Contact Info

Product

Resources

About

Cs₅([12]crown‐4)₂(O₃)₅: A Supramolecular Compound Containing the Confined Ozonide Partial Structure ${{{\hfill 1\atop \hfill \infty }}}${Cs₈(O₃)₁₀}²⁻

¹⁷O-ESR Evidence for Zeolite Matrix Isolation of a Square Planar ZnO₃ Ring Radical with C_2v Symmetry