Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes

Abstract

[EN] An unprecedented quantum tunneling effect has been observed in catalytic Si-H bond activations at room temperature. The cationic hydrido-silyl-iridium(III) complex, {Ir[SiMe(o-C6H4SMe)(2)](H)(PPh3)(THF)}[BAr4F], has proven to be a highly efficient catalyst for the hydrolysis and the alcoholysis of organosilanes. When triethylsilane was used as a substrate, the system revealed the largest kinetic isotopic effect (KIESi-H/Si-D=346 +/- 4) ever reported for this type of reaction. This unexpectedly high KIE, measured at room temperature, together with the calculated Arrhenius preexponential factor ratio (A(H)/A(D)=0.0004) and difference in the observed activation energy [(EaD -EaH )=34.07 kJ mol(-1)] are consistent with the participation of quantum tunneling in the catalytic process. DFT calculations have been used to unravel the reaction pathway and identify the rate-determining step. Aditionally, isotopic effects were considered by different methods, and tunneling effects have been calculated to be crucial in the process.