We report the characterization of the compound [K([2.2.2]crypt)]4[In8Sb13], which proves to contain a 1:1 mixture of [Sb@In8Sb12]3− and [Sb@In8Sb12]5−. The tri-anion displays perfect Th symmetry, the first completely inorganic molecule to do so, and contains eight equivalent In3+ centers in a cube. The gas-phase potential energy surface of the penta-anion has eight equivalent minima where the extra pair of electrons is localized on one In+ center, and these minima are linked by low-lying transition states where the electron pair is delocalized over two adjacent centers. The best fit to the electron density is obtained from a model where the structure of the 5− cluster lies close to the gas-phase transition state.
Author ORCID Identifier
Alexander I. Boldyrev https://orcid.org/0000-0002-8277-3669
Nikolay Tkachenko https://orcid.org/0000-0002-7296-4293
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NSF, Division of Chemistry (CHE)
Utah State University
NSF, Division of Chemistry (CHE) 1664379
Deciphering Delocalized Bonding in Excited States, Solvated Species and Novel 0-, 1-, 2-, and 3-Dimensional Chemical Systems
All manipulations and reactions were performed in a nitrogen atmosphere using standard Schlenk or glovebox techniques. En (Aldrich, 99%) and DMF (Aldrich, 99.8%) were freshly distilled by CaH2 prior to use. Tol (Aldrich, 99.8%) was distilled from sodium/benzophenone under nitrogen and stored under nitrogen. 2,2,2-crypt (4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo (8.8.8) hexacosane, purchased from Sigma-Aldirich, 98%) was dried in vacuum for one day prior to use. K5Sb4 was synthesized by heating a stoichiometric mixture of the elements at 800℃ for two days in a niobium tube. In(benzyl)3 was prepared according to literature methodology.
Liu, C., Tkachenko, N. V., Popov, I. A., Fedik, N., Min, X., Xu, C., Li, J., McGrady, J. E., Boldyrev, A. I., & Sun, Z. (2019). Structure and Bonding in [Sb@In 8 Sb 12 ] 3− and [Sb@In 8 Sb 12 ] 5−. Angewandte Chemie International Edition, 58(25), 8367–8371. https://doi.org/10.1002/anie.201904109
This work is licensed under a Creative Commons Attribution 4.0 License.
Boldyrev, A. I., & Tkachenko, N. (2021). Data from: Structure and Bonding in [Sb@In8Sb12]3− and [Sb@In8Sb12]5−. Utah State University. https://doi.org/10.26078/J4CM-PA56
Additional FilesREADME.txt (2 kB)
AdNDP_[Sb@In8Sb12]3- singlet_state.zip (6133 kB)
AdNDP_[Sb@In8Sb12]5- singlet_state.zip (12114 kB)
Supplementary_Information.pdf (1074 kB)
Deposit_Agreement.docx.pdf (630 kB)