Direct observation of a borane-silane complex involved in frustrated Lewis-pair-mediated hydrosilylations

作者：Houghton, Adrian Y.; Hurmalainen, Juha; Mansikkamaki, Akseli; Piers, Warren E.^*; Tuononen, Heikki M.

来源：Nature Chemistry, 2014, 6(11): 983-988.

DOI：10.1038/NCHEM.2063

• B(C6F5)(3)-CATALYZED HYDROSILYLATION
• SOLID-STATE
• DIHYDROGEN ACTIVATION
• HYDROGEN ACTIVATION
• FACILE ACTIVATION
• CARBON-MONOXIDE
• MECHANISM
• REDUCTION
• HYDROSILATION
• IMINES

Perfluorarylborane Lewis acids catalyse the addition of silicon-hydrogen bonds across C=C, C=N and C=O double bonds. This 'metal-free' hydrosilylation has been proposed to occur via borane activation of the silane Si-H bond, rather than through classical Lewis acid/base adducts with the substrate. However, the key borane/silane adduct had not been observed experimentally. Here it is shown that the strongly Lewis acidic, antiaromatic 1,2,3-tris(pentafluorophenyl)-4,5,6,7-tetrafluoro-1-boraindene forms an observable, isolable adduct with triethylsilane. The equilibrium for adduct formation was studied quantitatively through variable-temperature NMR spectroscopic investigations. The interaction of the silane with the borane occurs through the Si-H bond, as evidenced by trends in the Si-H coupling constant and the infrared stretching frequency of the Si-H bond, as well as by X-ray crystallography and theoretical calculations. The adduct's reactivity with nucleophiles demonstrates conclusively the role of this species in metal-free 'frustrated-Lewis-pair' hydrosilylation reactions.

• 出版日期2014-11