Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion, Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH- as Nucleophile

0523804 - ÚACH 2021 RIV CH eng J - Journal Article
Bakardjiev, Mario - El Anwar, Suzan - Bavol, Dmytro - Růžičková, Z. - Grüner, Bohumír
Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion, Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH- as Nucleophile.
Molecules. Roč. 25, č. 4 (2020), č. článku 814. E-ISSN 1420-3049
R&D Projects: GA ČR(CZ) GA18-27648S
Grant - others:AV ČR(CZ) L200321851
Program: Program podpory perspektivníchlidských zdrojů - postdoktorandů
Institutional support: RVO:61388980
Keywords : borane * carborane * dicarbollide ion * oxonium atom * nucleophilic substitution
OECD category: Inorganic and nuclear chemistry
Impact factor: 4.412, year: 2020
Method of publishing: Open access

Ring cleavage of cyclic ether substituents attached to a boron cage via an oxonium oxygen atom are amongst the most versatile methods for conjoining boron closo-cages with organic functional groups. Here we focus on much less tackled chemistry of the 11vertex zwitterionic compound [10-(0-(CH2-CH2)(2)O)-nido-7,8-C2B9H11] (1), which is the only known representative of cyclic ether substitution at nido-cages, and explore the scope for the use of this zwitterion 1 in reactions with various types of nucleophiles including bifunctional ones. Most of the nitrogen, oxygen, halogen, and sulphur nucleophiles studied react via nucleophilic substitution at the C1 atom of the dioxane ring, followed by its cleavage that produces six atom chain between the cage and the respective organic moiety. We also report the differences in reactivity of this nido-cage system with the simplest oxygen nucleophile, i.e., OH-. With compound 1, reaction proceeds in two possible directions, either via typical ring cleavage, or by replacement of the whole dioxane ring withOH at higher temperatures. Furthermore, an easy deprotonation of the hydrogen bridge in 1 was observed that proceeds even in diluted aqueous KOH. We believe this knowledge can be further applied in the design of functional molecules, materials, and drugs.
Permanent Link: http://hdl.handle.net/11104/0308097


Research data: CCDC