Access to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes

Jan Vrána, Josef Holub, Maksim A. Samsonov, Zdeňka Růžičková, Josef Cvačka, Michael L. McKee, Jindřich Fanfrlík, Drahomír Hnyk and Aleš Růžička ()
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Jan Vrána: University of Pardubice
Josef Holub: Institute of Inorganic Chemistry, Czech Academy of Sciences
Maksim A. Samsonov: University of Pardubice
Zdeňka Růžičková: University of Pardubice
Josef Cvačka: Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences
Michael L. McKee: Auburn University
Jindřich Fanfrlík: Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences
Drahomír Hnyk: Institute of Inorganic Chemistry, Czech Academy of Sciences
Aleš Růžička: University of Pardubice

Nature Communications, 2021, vol. 12, issue 1, 1-7

Abstract: Abstract Polyhedral boranes and heteroboranes appear almost exclusively as neutral or anionic species, while the cationic ones are protonated at exoskeletal heteroatoms or they are instable. Here we report the reactivity of 10-vertex closo-dicarbadecaboranes with one or two equivalents of N-heterocyclic carbene to 10-vertex nido mono- and/or bis-carbene adducts, respectively. These complexes easily undergo a reaction with HCl to give cages of stable and water soluble 10-vertex nido-type cations with protonation in the form of a BHB bridge or 10-vertex closo-type cations containing one carbene ligand when originating from closo-1,10-dicarbadecaborane. The reaction of a 10-vertex nido mono-carbene adduct with phosphorus trichloride gives nido-11-vertex 2-phospha-7,8-dicarbaundecaborane, which undergoes an oxidation of the phosphorus atom to P = O, while the product of a bis-carbene adduct reaction is best described as a distorted C2B6H8 fragment bridged by the (BH)2PCl2+ moiety.

Date: 2021
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DOI: 10.1038/s41467-021-25277-0

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