Collect. Czech. Chem. Commun. 2007, 72, 1725-1739
https://doi.org/10.1135/cccc20071725

Study of Proton-Deuterium Exchange in Ten-Vertex Boron Hydrides

Igor B. Sivaev*, Vikentii I. Bragin, Alexander V. Prikaznov, Pavel V. Petrovskii, Vladimir I. Bregadze, Oleg A. Filippov, Tatyana A. Teplinskaya, Alexei A. Titov and Elena S. Shubina*

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia

Abstract

The effect of electron-donating and electron-withdrawing substituents on the proton-deuterium exchange in derivatives of the closo-decaborate anion in methanol-d4 was studied. Introduction of the electron-donating hydroxy (alkoxy) group into the apical position of the boron cage strongly promotes the H-D exchange at the antipodal apical vertex, whereas introduction of the electron-withdrawing diazonium group stops the H-D exchange completely. The general order of the proton-deuterium exchange in equatorially-substituted derivatives [2-B10H9R]n- is 10 > 1 >> 7,8 > 4 > 3,5 ≈ 6,9. Formation of dihydrogen bonds between 1- and 2-hydroxy derivatives of the closo-decaborate anion and alcohols was investigated and their possible role in the H-D exchange was discussed.

Keywords: Boranes; Boron clusters; closo-Decaborate; Proton-deuterium exchange; Isotope effects; Hydrogen bonds; NMR spectroscopy; IR spectroscopy.

References: 46 live references.