Nonredox Metal-Ion-Accelerated Olefin Isomerization by Palladium(II) Catalysts: Density Functional Theory (DFT) Calculations Supporting the Experimental Data

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• 作者：Ahmed M. Senan ; Shuhao Qin ; Sicheng Zhang ; Chenling Lou ; Zhuqi Chen ; Rong-Zhen Liao ; Guochuan Yin
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：July 1, 2016
• 年：2016
• 卷：6
• 期：7
• 页码：4144-4148
• 全文大小：314K
• 年卷期：0
• ISSN：2155-5435

文摘

Redox metal-ion-catalyzed olefin isomerization represents one of the important chemical processes. This work illustrates that nonredox metal ions can sharply accelerate Pd(II)-catalyzed olefin isomerization, while Pd(II) alone is very sluggish. Nuclear magnetic resonance (NMR) and ultraviolet–visible light (UV-vis) characterizations disclosed that the acceleration effect originates from the formation of heterobimetallic Pd(II) species with added nonredox metal ions, which improves the C–H activation capability of the Pd(II) moiety. Density functional theory (DFT) calculations further confirmed the sharp decrease of the energy barrier in C–H activation by the heterobimetallic Pd(II)/Al(III) species.