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在环境条件下,空气中分散于脱铝Y沸石上的PdO催化的铃木耦合反应。

Suzuki Coupling Reactions Catalyzed by PdO Dispersed on Dealuminated Y Zeolite in Air under Ambient Conditions.

作者信息

Okumura Kazu, Mushiake Takumi, Matsui Yu, Ishii Akira

机构信息

Department of Applied Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano-machi, Hachioji City, Tokyo (Japan).

Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, 4-101 Koyama-cho Minami, Tottori City, Tottori (Japan).

出版信息

Chemphyschem. 2015 Jun 8;16(8):1719-26. doi: 10.1002/cphc.201500118. Epub 2015 Mar 27.

Abstract

Suzuki coupling reactions are performed using PdO loaded on dealuminated Y (USY) zeolite. The reaction between bromobenzene and phenylboronic acid is complete in 15 min at room temperature in air, with a turnover number of 1300. The reaction can be repeated at least five times by using 1 wt % Pd. Inductively coupled plasma analysis does not reveal the dissolution of Pd from products, even if the reaction is repeated up to four times. Pd K-edge extended X-ray absorption fine structure analysis reveals the presence of molecular-like PdO and a mixture of Pd(0) -PdO before and after the reaction, respectively. This is probably because Pd stabilized by Al sites is present at the II sites of the Y-type zeolite, as estimated using first-principles calculations. Conversely, Pd species change to PdO clusters after repeated reactions in air using the thermally treated sample.

摘要

使用负载在脱铝Y(USY)沸石上的PdO进行铃木偶联反应。溴苯与苯硼酸之间的反应在室温下于空气中15分钟内完成,周转数为1300。使用1 wt%的Pd,该反应可至少重复五次。电感耦合等离子体分析未显示Pd从产物中溶解出来,即使反应重复多达四次。Pd K边扩展X射线吸收精细结构分析分别揭示了反应前后类分子PdO以及Pd(0)-PdO的混合物的存在。这可能是因为如通过第一性原理计算所估计的,由Al位点稳定的Pd存在于Y型沸石的II位点。相反,使用经过热处理的样品在空气中重复反应后,Pd物种转变为PdO簇。

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