期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 36, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202204558
关键词
Homogeneous Catalysis; Iridium; Quantum Tunneling; Silanes
资金
- Universidad del Pais Vasco (UPV/EHU) [GIU13/06]
- Ministerio de Economia y Competitividad [PID2019-111281GB-00]
- Gobierno Vasco [IT1880-19, IT1254-19]
- Diputacion Foral de Gipuzkoa [OF215/2016]
- IKERBASQUE
An unprecedented quantum tunneling effect has been observed in catalytic Si-H bond activations at room temperature. Both experimental and computational studies showed that quantum tunneling plays a crucial role in the catalytic process, affecting the activation energy and reaction rate significantly.
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.
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