Catalytic Hydrogen Generation from the Hydrolysis of Silanes by Ruthenium Complexes

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.

二聚体钌(II)配合物Ru₂(CO)₄L₂X₄（其中L为CO或三苯基膦(PPh₃)，X为Cl或Br）可催化硅烷水解反应，生成氢气与硅醇，在室温条件下的转化数（TON）超过10⁴。氘代实验与质谱研究证实，氢气的两个氢原子分别源自水分子与硅烷分子。反应初期可通过核磁共振波谱（NMR）检测到氢化钌中间体；催化反应完成后，可记录到更稳定的配合物如Ru(CO)₂(PPh₃)(THF)Br₂与Ru(CO)₂(PPh₃)₂(H)Br的傅里叶变换红外光谱（FTIR）。研究人员基于上述实验数据，提出了钌催化硅烷水解的反应机理。