Eleven-vertex carboranes

Grimes, Russell N.

doi:10.1016/b978-0-12-374170-7.00011-2

Cited by 2 publications

(1 citation statement)

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“…Eleven vertex 7,8-Dicarba-nido-dodecahydroundecaborate(1−) ion [1] belongs to the most studied boron cluster anions due to its easy availability from ortho-carborane [2], open pentagonal C 2 B 3 plane with three stereochemically distinctive sites for substitution and an extra hydrogen atom sitting on it [3,4]. It is well recognized that the coupling of the [nido-7,8-C 2 B 9 H 12 ] − ion with tetrahydrofuran and dioxane promoted by various metal halides, such as FeCl 3 [5] or HgCl 2 [6,7], yields the neutral zwitterionic compounds [10-(CH 2 ) 4 O)-nido-7,8-C 2 B 9 H 11 ] or [10-(O-(CH 2 -CH 2 ) 2 O)-nido-7,8-C 2 B 9 H 11 ] (1).…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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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 11-vertex zwitterionic compound [10-(O-(CH2-CH2)2O)-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 with -OH 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.

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