Using NMR and ESI-MS to Probe the Mechanism of Silane Dehydrocoupling Catalyzed by Wilkinson's Catalyst

作者：Jackson Sarah M; Chisholm Danielle M; McIndoe J Scott^*; Rosenberg Lisa

来源：European Journal of Inorganic Chemistry, 2011, (3): 327-330.

DOI：10.1002/ejic.201001165

• Silanes
• Reaction mechanisms
• NMR spectroscopy
• Electrospray ionization mass spectrometry

The reaction of Wilkinson's catalyst Rh(PPh(3))(3)Cl (1) with 1-2 equiv. of di-n-hexylsilane gives rise to a complex mixture of products, which has been analyzed by (31)P{(1)H} NMR and shown to include the hydrido complex Rh(PPh(3))(3)H (3). Continuous sampling of the 1:1 reaction mixture by ESI-MS provided time-dependent speciation that tracks the formation of 3 at the expense of the initial silane oxidative addition product [Rh(PPh(3))(2)(Cl)(H){Si(nHex)(2)H}] (2), the subsequent 1st order disappearance of 3, and the formation of other, minor side-products. Our results provide insight into established activity of 1 for catalytic dehydrocoupling of di-n-hexylsilane, and implicate complex 3 as the active species in this catalysis.

• 出版日期2011-1