Jump to main content
Jump to site search

Issue 45, 2015
Previous Article Next Article

Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron

Author affiliations

Abstract

The inner salts x-H3N-closo-1-CB11H11 (x = 12, 2) and 7-H3N-12-F-closo-1-CB11H11 were fluorinated with elemental fluorine in anhydrous hydrogen fluoride to give the B-perfluorinated ammonio derivatives 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2). Deprotonation of the ammonio group yielded the corresponding amino-functionalized anions [1-H-x-H2N-closo-1-CB11F10] (x = 12, 7, 2) that were isolated as [Et4N]+ salts. Hydrolysis of the highly fluorinated inner salts 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2) is very slow in acidic aqueous solutions. This stability of the ammonio derivatives is unprecedented because the related fluorinated anion [1-H2N-closo-1-CB11F11] is immediately hydrolyzed to simple boron species in the presence of aqueous acids. The ammonio derivatives 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2) are much more acidic compared to their non-fluorinated counterparts as assessed from potentiometric titrations and DFT calculations. The inner salts and the anions were characterized by NMR and vibrational sepectroscopy. Solid-sate structures of 1-H-12-H3N-closo-1-CB11F10·H2O, 1-H-7-H3N-closo-1-CB11F10·diglyme, 1-H-2-H3N-closo-1-CB11F10·0.5H2O, 7-H3N-12-F-closo-1-CB11H10·(CH3)2CO and [Et4N][1-H-12-H2N-closo-1-CB11F10] were determined by single-crystal X-ray diffraction.

Graphical abstract: Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron

  • This article is part of the themed collection: Fluorine
Back to tab navigation

Supplementary files

Publication details

The article was received on 31 May 2015, accepted on 07 Jul 2015 and first published on 07 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT02055G
Citation: Dalton Trans., 2015,44, 19576-19586
  •   Request permissions

    Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron

    S. Z. Konieczka, M. Drisch, K. Edkins, M. Hailmann and M. Finze, Dalton Trans., 2015, 44, 19576
    DOI: 10.1039/C5DT02055G

Search articles by author

Spotlight

Advertisements