ACS Catalysis p. 1860 - 1867 (2017)
Update date:2022-08-29
Topics:
Fu, Fangyu
Xiang, Ji
Cheng, Hao
Cheng, Longjiu
Chong, Hanbao
Wang, Shuxin
Li, Peng
Wei, Shiqiang
Zhu, Manzhou
Li, Yadong
The palladium-catalyzed Suzuki-Miyaura coupling reaction is one of the most versatile and powerful tools for constructing synthetically useful unsymmetrical aryl-aryl bonds. In designing a Pd cluster as a candidate for efficient catalysis and mechanistic investigations, it was envisaged to study a case intermediate between, although very different from, the "classic" Pd(0)Ln and Pd nanoparticle families of catalysts. In this work, the cluster [Pd3Cl(PPh2)2(PPh3)3]+[SbF6]- (abbreviated Pd3Cl) was synthesized and fully characterized as a remarkably robust framework that is stable up to 170 °C and fully air-stable. Pd3Cl was found to catalyze the Suzuki-Miyaura C-C crosscoupling of a variety of aryl bromides and arylboronic acids under ambient aerobic conditions. The reaction proceeds while keeping the integrity of the cluster framework all along the catalytic cycle via the intermediate Pd3Ar, as evidenced by mass spectrometry and quick X-ray absorption fine structure. In the absence of the substrate under the reaction conditions, the Pd3OH species was detected by mass spectrometry, which strongly favors the "oxo-Pd" pathway for the transmetalation step involving substitution of the Cl ligand by OH followed by binding of the OH ligand with the arylboronic acid. The kinetics of the Suzuki- Miyaura reaction shows a lack of an induction period, consistent with the lack of cluster dissociation. This study may provide new perspectives for the catalytic mechanisms of C-C cross-coupling reactions catalyzed by metal clusters.
View MoreChengdu Cogon Bio-tech Co., Ltd.
Contact:86-28-85171192
Address:NO.52.YongFeng Rd. Chengdu,610041,P.R.China.
Shanghai SMEC Trading Co., Ltd.
website:http://www.shanghaismec.com
Contact:+86-21-68811293
Address:ROOM 1101,NO.800 SHANGCHENG RD,SHANGHAI,CHINA
Jinan Boss Chemical Industry Co., Ltd.
website:http://www.chemboss.com.cn
Contact:+86-531-58591595
Address:No2.Hualong Road, Jinan, China
Shenzhen Tianyuan Pharmaceutical Technology Co., Ltd
website:http://www.tianpharm.com
Contact:86-755-23284190
Address:B302,2 unit, Jin Lian Building, No. 134 Qianjin 2 Road, Taoyuan village, Xixiang Street, Baoan,Shenzhen,China
Oren Hydrocarbons (Qingdao) Co., Ltd.
Contact:+86-532-68607667-801
Address:Room 3 # 302, No.9 Qingyun Road, Qingdao, China
Doi:10.5935/0103-5053.20140254
(2014)Doi:10.1039/d1ra00205h
(2021)Doi:10.1021/jo001316s
(2000)Doi:10.1007/s11696-021-01603-0
(2021)Doi:10.1016/0022-328X(85)87280-6
(1985)Doi:10.1021/ja00494a023
(1978)