Collect. Czech. Chem. Commun. 2002, 67, 953-964

Synthesis of 12-Hydroxy and 12-Dioxane Derivatives of the closo-1-Carbadodecaborate(1-) Ion. Variations on the Plešek's Cobalt Bis(dicarbollide) Pattern

Bohumír Grünera,*, Ivana Císařováb, Josef Čáslavskýc, Bernard Bonnetotd and David Cornud

a Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, 250 68 Řež, Czech Republic
b Department of Chemistry, Faculty of Natural Science of the Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
c Institute of Analytical Chemistry, Academy of Sciences of the Czech Republic, Veveří 97, 611 42 Brno, Czech Republic
d Laboratoire des Multimatériaux et Interfaces (UMR CNRS 5615), UCB Lyon I, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne cedex, France


Synthesis of two new B(12) substituted derivatives of the closo-[1-CB11H12]- anion (1) is reported. The zwitterionic derivative containing dioxane ring {12-[O(CH2CH2)2O]+-1-CB11H11-}0 (2) was obtained in moderate yield using reaction of anion 1 with dioxane as solvent, induced by dimethyl sulfate. The anion [12-(HO)-1-CB11H11]- (3) was obtained in high yield upon treatment of the parent anion with 80% H2SO4 at high temperature. Both compounds containing reactive functionalities were designed to serve as useful synthons for a variety of synthetic purposes. The compounds were characterized by 11B and 1H high-field NMR, IR spectroscopy, mass spectrometry, melting points and TLC. Molecular structure of compound 2 was determined by single crystal X-ray diffraction analysis.

Keywords: Boranes; Carboranes; Monocarbaboranes; closo-1-Carbadodecaborate(1-) ion; BNCT; X-Ray diffraction; Crystal structure.

References: 44 live references.