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Proton-assisted hydrogen activation on polyhedral cations

Autor Calvo, Beatriz ; Macías, Ramón ; Artigas, María José ; Lahoz, Fernando J. ; Oro, Luis A.
Palabras clave Cations
Fecha de publicación 2013
Citación Chemistry - A European Journal 19(12): 3905-3912 (2013)
ResumenThe treatment of [1,1-(PR3)2-3-(Py)-closo-1,2- RhSB9H8] (PR3=PMe3 (2) or PPh 3 and PMe3 (3); Py=pyridine) with triflic acid (TfOH) affords [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-1,2-RhSB 9H8]+ (PR3=PMe3 (4) or PMe3 and PPh3 (5)). These products result from the protonation of the 11-vertex closo-cages along the Rh(1)-B(3) edge. These unusual cationic rhodathiaboranes are stable in solution and in the solid state and they have been fully characterized by multinuclear NMR spectroscopy. In addition, compound 5 was characterized by single-crystal X-ray diffraction. One remarkable feature in these structures is the presence of three {Rh(PPh 3)(PMe3)}-to-{ηn-SB9H 8(Py)} (n=4 or 5) conformers in the unit cell, thus giving an uncommon case of conformational isomerism. [1,1-(PPh3) 2-3-(Py)-closo-1,2-RhSB9H8] (1), that is, the bis-PPh3-ligated analogue of compounds 2 and 3, is also protonated by TfOH, but, in marked contrast, the resulting cation, [1,3-μ-(H)-1,1- (PPh3)2-3-(Py)-1,2-RhSB9H8] + (6), is attacked by a triflate anion with the release of a PPh 3 ligand and the formation of [8,8-(OTf)(PPh3)-9-(Py)- nido-8,7-RhSB9H9] (9). The result is an equilibrium that involves cationic species 6, neutral OTf-ligated compound 9, and [HPPh 3]+, which is formed upon protonation of the released PPh3 ligand. The resulting ionic system reacts readily with H 2 to give cationic species [8,8,8-(H)(PPh3) 2-9-(Py)-nido-8,7-RhSB9H9]+ (7). This reactivity is markedly higher than that previously found for compound 1 and it introduces a new example of proton-assisted H2 activation that occurs on a polyhedral boron-containing compound.
Versión del editorhttp://dx.doi.org/10.1002/chem.201203925
URI http://hdl.handle.net/10261/111362
Identificadoresdoi: 10.1002/chem.201203925
issn: 0947-6539
e-issn: 1521-3765
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