Catalytic Hydrogen Generation from the Hydrolysis of Silanes by Ruthenium Complexes

Abstract

Dimeric Ru(II) complexes Ru2(CO)4L2X4 (L = CO or PPh3; X = Cl or Br) have been found to catalyze the hydrolysis of silanes to produce hydrogen gas and silanols with turnover numbers in excess of 104 at room temperature. Deuteration and mass spectrometric studies have established that the hydrogen gas originates from one hydrogen atom from water and the other from silane. Ruthenium hydride intermediates have been detected in the NMR spectrum during the early stage of the reaction, while the FTIR spectra of more stable complexes such as Ru(CO)2(PPh3)(THF)Br2 and Ru(CO)2(PPh3)2(H)Br have been recorded upon completion of catalysis. A mechanism has been proposed to account for the ruthenium-catalyzed silane hydrolysis based on the experimental data.

Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

“…As haloruthenium carbonyls such as Ru 2 (CO) 4 (PPh 3 ) 2 Br 4 , Ru 2 (CO) 6 Br 4 and Ru 2 (CO) 6 I 4 are known to activate SieH bonds [18], we have prepared these complexes using reported methods [35] for the SieS coupling reaction. However the coupling is found to proceed less effectively for each of them compare to Ru 3 (CO) 12 .…”

“…Ruthenium carbonyl complexes have also been reported to generate hydrogen from a silane/water mixture [17,18] and from formic acid [19]. The hydrogen gas produced can be used in a variety of reactions, of which one of the most well-studied reaction involves the hydrogenation of unsaturated compounds catalysed by palladium (II) [20] or iridium (I) [21] complexes.…”

Addition of pyrroles onto terminal alkynes catalyzed by a dinuclear ruthenium (II) complex

“…The ruthenium complex, Ru 2 (CO) 4 (PPh 3 ) 2 Br 4 and Ru 2 (CO) 6 Br 4 , were prepared from Ru 3 (CO) 9 (PPh 3 ) 3 and Ru 3 (CO) 12 respectively according to literature methods and characterised by FTIR spectroscopy [20].…”

Can main group systems act as superior catalysts for dihydrogen generation reactions? A computational investigation

“…[21][22][23][60][61][62][63][64][65] Recently, Parkin and co-workers have reported a catalytic cycle with the zinc hydride catalyst: [Tris(2-pyridylthio)methyl]zinc hydride ([κ 3 -Tptm]ZnH) for the hydrolysis and alcoholysis of phenylsilanes. Most of the reported catalytic cycles for this reaction involve transition metal based systems, employing precious metals such as rhodium, rhenium, platinum and gold.…”