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Issue 19, 2015
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[1,1-(η2-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8]: conformational lability and reactivity with H2 upon protonation

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Metallaheteroboranes are versatile compounds that can be conveniently modified and eventually tailored by ligand modification at either the metal centre or the boron vertices. Recently, we have discovered that protonation of some rhodathiaboranes affords cationic clusters with interesting reaction chemistry. In order to tune the reactivity of some of these polyhedral boron-based compounds, we have prepared air-stable orange [1,1-(η2-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8] (2) by the treatment of the known hydridorhodathiaborane [8,8,8-(H)(PPh3)2-9-(NC5H5)-nido-8,7-RhSB9H9] (1) with dppe. The new 11-vertex rhodathiaborane, 2, reacts readily with triflic acid (TfOH) in CH2Cl2 to give orange cationic [8,8-(η2-dppe)-9-(NC5H5)-nido-8,7-RhSB9H9]+ (3). VT NMR experiments have allowed the characterization of a structural closonido tautomerism, which involves hapticity changes in the ligation of the {SB9H9-(NC5H5)} moiety to the {Rh(dppe)} fragment, with the proton moving between the Rh(1)–B(3) and the B(9)–B(10) edges of the closo- and nido-isomers, respectively. The proton enhances the stereochemical non-rigidity and Lewis acidity of 3versus the neutral 2. This modification of the chemical and structural basis permits the efficient heterolytic splitting of the H–H bond, leading to the formation of new hydridorhodathiaborane isomers [8,8,8-(H)(η2-dppe)-μ-8,9-(H)-9-(NC5H5)-nido-8,7-RhSB9H10]+ (4) that are in equilibrium with the reactants, H2 and 3.

Graphical abstract: [1,1-(η2-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8]: conformational lability and reactivity with H2 upon protonation

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Supplementary files

Article information

20 Jan 2015
07 Apr 2015
First published
08 Apr 2015

Dalton Trans., 2015,44, 9004-9013
Article type
Author version available

[1,1-(η2-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8]: conformational lability and reactivity with H2 upon protonation

A. C. Mateo, B. Calvo, R. Macías, M. J. Artigas, F. J. Lahoz and L. A. Oro, Dalton Trans., 2015, 44, 9004
DOI: 10.1039/C5DT00288E

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