English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/186699
Share/Impact:
Statistics
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE
Exportar a otros formatos:

Title

Decaborane anion tautomerism: ion pairing and proton transfer control

AuthorsPérez Solsona, Sandra CSIC ORCID ; Sanz Miguel, Pablo J. CSIC ORCID; Macías, Ramón CSIC ORCID
Issue Date2018
PublisherRoyal Society of Chemistry (UK)
CitationDalton Transactions 47(16): 5850-5859 (2018)
AbstractThe reaction of 1,8-bis(dimethylamino)naphthalene-which is often referred by the trade name Proton-Sponge (PS)-with decaborane in hexane afforded [HPS][B10H13] (1) salt as a pale-yellow precipitate. Variable-temperature NMR studies allowed the full assignment of 1H and 11B spectra for this familiar ten-vertex polyhedral anion. In addition, this work reveals that an increase in the temperature leads to the intramolecular exchange of three B-H-B hydrogen atoms around the hexagonal face of the boat-shaped cluster. This previously unrecognised H-tautomerism complements the long-known low-energy proton exchange of only one of the bridging hydrogen atoms. The temperature dependent proton fluxional behaviour controls the molecular environment of the polyhedral cage, averaging the negative charge of the anion. The result is a debilitation of the cation-anion interactions in solution, favouring the transfer of the proton from the organic aromatic cation, [HPS]+, to the polyhedral anion, [B10H13]-. This proton transfer affords Proton-Sponge and decaborane, increasing the entropy of the system and sustaining an equilibrium which at high temperatures shifts toward the neutral reactants and at low temperatures moves toward the ionic products. A single X-ray diffraction analysis of 1 is discussed.
Publisher version (URL)https://doi.org/10.1039/C8DT00610E
URIhttp://hdl.handle.net/10261/186699
DOIhttp://dx.doi.org/10.1039/c8dt00610e
ISSN1477-9226
E-ISSN1477-9234
Appears in Collections:(ISQCH) Artículos
Files in This Item:
File Description SizeFormat 
accesoRestringido.pdf59,24 kBAdobe PDFThumbnail
View/Open
Show full item record
Review this work
 

Related articles:


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.