Cation-cation interactions often occur between molecular cations of transition metals and f-elements (so-called yl cations). They are distinguished as a separate type of intermolecular interactions, since without taking them into account, cations usually repel each other in accordance with Coulomb's law.

Cation-cation interactions in f-elements.

Of particular interest are cation-cation interactions between actinide cations - uranium, in the form of uranyl UO22+, neptunium in the form of neptunoyl NpO22+, plutonium and americium, which are essentially a manifestation of specific complex formation.[1] They are a special case of intermolecular interactions that occur in molecular ions. It was first discovered when studying the behavior of netunium(V) compounds in solutions of uranyl perchlorate.[2] Great impact to crystallochemistry of cation-cation bonds was made by Mikhail Grigoriev.

The cation-cation interaction [NpO2]+ determines the crystal structure of Np(V) compounds, and the strength of cation-cation bonds between neptunoyl ions in a solid is comparable to the strength of ordinary bonds with acid ligands,[3] although in an aqueous solution, apparently, the role There are somewhat fewer of these connections. In an organic solution, the intensity of C-C interactions can remain high [1]. In the absence of mutual coordination of neptunium ions, Np(V) compounds can exhibit both structural similarity with An(VI) compounds and fundamental differences (showing a tendency to unite Np coordination polyhedra through common equatorial edges. Cation-cation interactions can be detected not only by data from structural studies, but also according to vibrational spectroscopy data.[4] For uranyl, cation-cation interactions are also recorded in the gas phase.[5]

Cation-cation interactions for transition metal cations

For transition metals, cation-cation interactions appear in nitrene complexes.[6] Nitrenium ligands provide an excellent platform for the simple and efficient synthesis of extremely rare complexes that have positively charged ligands coordinated to positively charged metals to form stable cation-cation and cation-dication coordination bonds.

References

  1. ↑ Krot, Nikolai N; Grigoriev, Mikhail S (2004-01-31). "Cation–cation interaction in crystalline actinide compounds". Russian Chemical Reviews. 73 (1): 89–100. doi:10.1070/RC2004v073n01ABEH000852. ISSN 0036-021X.
  2. ↑ Sullivan, J. C.; Hindman, J. C.; Zielen, A. J. (August 1961). "Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media 1". Journal of the American Chemical Society. 83 (16): 3373–3378. doi:10.1021/ja01477a004. ISSN 0002-7863.
  3. ↑ Charushnikova, I. A.; Krot, N. N.; Grigor'ev, M. S. (September 2014). "Cation-cation interaction in mixed-valent An(IV)/Np(V) tribromoacetates [An(NpO2)(H2O)3(CBr3COO)5]·CBr3COOH·nH2O, An = Th(IV), Np(IV)". Radiochemistry. 56 (5): 468–475. doi:10.1134/S1066362214050026. ISSN 1066-3622.
  4. ↑ Pyrch, Mikaela M.; Augustine, Logan J.; Williams, James M.; Mason, Sara E.; Forbes, Tori Z. (2022). "Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study". Dalton Transactions. 51 (12): 4772–4785. doi:10.1039/D2DT00200K. ISSN 1477-9226.
  5. ↑ Feng, Rulin; Glendening, Eric D.; Peterson, Kirk A. (2019). "Actinyl cation–cation interactions in the gas phase: an accurate thermochemical study". Physical Chemistry Chemical Physics. 21 (15): 7953–7964. doi:10.1039/C9CP00760A. ISSN 1463-9076.
  6. ↑ Tulchinsky, Yuri; Kozuch, Sebastian; Saha, Prasenjit; Botoshansky, Mark; Shimon, Linda J. W.; Gandelman, Mark (2014). "Cation–cation bonding in nitrenium metal complexes". Chemical Science. 5 (4): 1305. doi:10.1039/c3sc53083c. ISSN 2041-6520.
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.