Citation: Zhang Qi, Liu Ao, Yu Haizhu, Fu Yao. Hydride Source in Ethers Hydrosilylation Reaction Catalyzed by Brookhart's Ir(Ⅲ) Pincer Complex[J]. Acta Chimica Sinica, ;2018, 76(2): 113-120. doi: 10.6023/A17070328 shu

Hydride Source in Ethers Hydrosilylation Reaction Catalyzed by Brookhart's Ir(Ⅲ) Pincer Complex

Zhang Qi ^a,b ,
Liu Ao ^c ,
Yu Haizhu ^c,, ,
Fu Yao ^a,,

a.
Department of Chemistry, University of Science and Technology of China, Hefei 230026
b.
Institute of Industry & Equipment Technology, Hefei University of Technology, Hefei 230009
c.
School of Chemistry & Chemical Engineering, Anhui University, Hefei 230601

Corresponding author: Yu Haizhu, yuhaizhu@ahu.edu.cn Fu Yao, fuyao@ustc.edu.cn
Received Date: 3 September 2017
Available Online: 28 February 2017
Fund Project: the National Natural Science Foundation of China 21572212Project supported by the National Natural Science Foundation of China (Nos. 21572212, 21672001, 21702041), Joint Foundation of National Natural Science Foundation of China and Academy of Engineering Physics (No. U1530262), and the supercomputing system of National Supercomputing Center in Shenzhen and USTCthe National Natural Science Foundation of China 21702041the National Natural Science Foundation of China 21672001Joint Foundation of National Natural Science Foundation of China and Academy of Engineering Physics U1530262

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The hydrosilylative reduction with silane is a popular defunctionalization strategy to convert biomass into chemicals and energies because of the mild reaction conditions. Among these, the reduction of C-O bond is particularly important because of its application in sugar biomass reduction. The (C₆F₅)₃ B/silane catalytic system has been frequently used in the reduction of C-O bonds in the past years. However, Brookhart et al. reported alkyl ethers reduction by using Ir(Ⅲ) pincer catalyst and reductant HSiEt₃. This work provides a novel hydrosilylation catalyst for C-O reduction and an effective method for sugar biomass deoxygenation. According to the previous mechanistic proposals on similar Ir catalysed hydrosilylation reactions, the iridium dihydride complex, iridium silyl hydride complex, silane adduct iridium complex and iridium silyl trihydride complex might possibly act as the hydride source. We carried out the theoretical study on Brookhart's Ir(Ⅲ) Pincer Complex/HSiEt₃ catalyzed hydrosilylation reaction of EtOEt yielding ethane and EtOSiEt₃. The density functional theory (DFT) calculations in our study indicate that the iridium dihydride complex is the best hydride source. Our calculation result is consistent well with experimental observations in Brookhart's experiment. For example, the phenomenon that adding iridium dihydride complex into the reaction system increases the reaction rate is understandable because the complex is involved in the rate-determining step. From the Distortion/Interaction analysis, we found that hydride transfer steps on the other three possible hydride sources are disfavoured by the HSiEt₃/-SiEt₃ group (derived from HSiEt₃) bonded with Ir center. The iridium silyl hydride complex is unfavourable because the Ir-H bond is strengthened and the pincer ligand is distorted. For the silane adduct iridium complex, the coordination of HSiEt₃ destabilizes iridium complex intermediate for entropy increases and trans effect, and destabilizes the related transition state by damaging its pincer ligand. Further, the corresponding hydride transfer transition state from iridium silyl trihydride is highly unstable and Si-H bond always reform automatically. What's more important, the moderate bond dissociation energy of Ir-hydride, small steric hindrance and the promotion effect of SiEt₃ group coordination with ether all facilitate the hydride transfer on the iridium dihydride complex.
- hydrosilylation,
- iridium,
- hydride,
- pincer,
- DFT
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