Borane and heteroborane clusters have been known as neutral or anionic species. In contrast to them, several ten-vertex monocationic nido and closo dicarbaborane-based systems have recently emerged from the reaction of the parent bicapped-square antiprismatic dicarbaboranes with N-heterocyclic carbenes followed by the protonization of the corresponding nido intermediates. The expansion of these efforts has afforded the very first closo-dicationic octahedral phosphahexaborane along with new closo-monocationic pnictogenahexaboranes of the same shapes. All are the products of the one-pot procedure that consists in the reaction of the same carbenes with the parent closo-1,2-Pn2B4Br4 (Pn = As, P). Whereas in the case of phosphorus such a monocation appears to be a mixture of stable intermediates, and arsenahexaboranyl monocation has occurred as the final product, all of them without using any subsequent reaction. The well-established DFT/ZORA/NMR approach has unambiguously confirmed the existence of these species in solution, and computed electrostatic potentials have revealed the delocalization of the positive charge in these monocations and in the very first dication, namely within the octahedral shapes in both cases.

Department of Chemistry and Biochemistry Auburn University Auburn AL 36849 USA

Institut für Chemie Universität Hohenheim Garbenstrasse 30 D 70599 Stuttgart Germany

Institute of Inorganic Chemistry of the Czech Academy of Sciences CZ 250 68 Husinec Řež Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 CZ 166 10 Praha 6 Czech Republic

Wilhelm Ostwald Institut für Physikalische und Theoretische Chemie Universität Leipzig Linnéstrasse 2 04103 Leipzig Germany

Zobrazit více v PubMed

Huynh H. A. Chem. Rev. 2018;118:9457. PubMed

For example Fleming I., Frontier Orbitals and Organic Chemical Reactions, John Wiley and Sons, Chichester, Sussex, UK, 1976

Hnyk D. and Wann D. A., Boron: the Fifth Element Challenges and Advances in Computational Chemistry and Physics, ed. D.Hnyk, M. L.McKee, 2016, vol. 20, ch. 2 and the extensive references therein

Melichar P. Hnyk D. Fanfrlík J. Phys. Chem. Chem. Phys. 2018;20:4666. PubMed

Schleyer P. v. R. Najafian K. Mebel A. M. Inorg. Chem. 1998;37:6765. PubMed

Hnyk D. Všetečka V. Drož L. Exner O. Collect. Czech. Chem. Commun. 2001;66:1375.

Hnyk D. Jayasree E. G. J. Comput. Chem. 2013;34:656. PubMed

Perumalla D. S. Ghorai S. Pal T. Hnyk D. Holub J. Jemmis E. D. J. Comput. Chem. 2023;44:256. PubMed

Willans C. E. Kilner C. A. Fox M. A. Chem.–Eur. J. 2010;16:10644. PubMed

Vrána J. Holub J. Růžičková Z. Fanfrlík J. Hnyk D. Růžička A. Inorg. Chem. 2019;58:2471. PubMed

Vrána J. Holub J. Samsonov M. A. Růžičková Z. Cvačka J. McKee M. L. Fanfrlík J. Hnyk D. Růžička A. Nat. Commun. 2021;12:4971. PubMed PMC

Keller W. Sneddon L. G. Einholz W. Gemmler A. Chem. Ber. 1992;125:2343.

Keller W. Einholz W. Rudolph D. Schleid T. Z. Anorg. Allg. Chem. 2017;643:664.

Keller W. Hofmann M. Anorg Z. Allg. J. Chem. 2017;643:729.

Keller W. Ballmann J. Sárosi M. B. Fanfrlík J. Hnyk D. Angew. Chem., Int. Ed. 2023;62:e2022119018. PubMed

Keller W. Hofmann M. Sárosi M. B. Fanfrlík J. Hnyk D. Inorg. Chem. 2022;61:16565. PubMed

Braunschweig H. Dewhurts R. D. Hammond K. Mies J. Radacki K. Vargas A. Science. 2012;336:1420. PubMed

Köppe R. Schnöckel H. Chem. Sci. 2015;6:1199. PubMed PMC

Fanfrlík J. Hnyk D. Crystals. 2018;8:390.

Waters J. P. Everitt T. A. Myers K. Goicoechea J. M. Chem. Sci. 2016;7:6981. PubMed PMC

Heřmánek S. Hnyk D. Havlas Z. J. Chem. Soc., Chem. Commun. 1989:1859.

Bühl M. Schleyer P. v. R. Havlas Z. Hnyk D. Heřmánek S. Inorg. Chem. 1991;30:3107.

Kruve A. Kaupmees K. J. Am. Soc. Mass Spectrom. 2017;28:887. PubMed

Xu C. Guo H. Breitbach Z. S. Armstrong D. W. Anal. Chem. 2014;86:2665. PubMed

Kruve A. Kaupmees K. J. Am. Soc. Mass Spectrom. 2017;28:887. PubMed

Nagy L. Nagy T. Deák G. Kuki Á. Purgel M. Narmandakh M. Iván B. Zsuga M. Kéki S. J. Am. Soc. Mass Spectrom. 2016;27:432. PubMed

Grimme S. Antony J. Ehrlich S. Krieg H. J. Chem. Phys. 2010;132:154104. PubMed

Maué D. Strebert P. H. Bernhard D. Rösel S. Schreiner P. R. Gerhards M. Angew. Chem., Int. Ed. 2021;60:11305. PubMed PMC

Baranac-Stojanovic M. RSC Adv. 2014;4:308.

See e.g.Wade K., Electron Deficient Compounds, Nelson, London, 1971

Morrison J. A. Chem. Rev. 1991;91:35.

Knizia G. J. Chem. Theory Comput. 2013;9:4834. PubMed

Gray M. Bowling P. E. Herbert J. M. J. Chem. Theory Comput. 2022;18:6742. PubMed

Kee M. L. J. Am. Chem. Soc. 1988;110:5317.