Revelation of the Photoactive Species in the Photocatalytic Dimerization of 伪-Methylstyrene by a Dinuclear Ruthenium鈥揚alladium Complex

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• 作者：Kei Murata ; Akiko Inagaki ; Munetaka Akita ; Jean-Fran莽ois Halet ; Karine Costuas
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 15, 2013
• 年：2013
• 卷：52
• 期：14
• 页码：8030-8039
• 全文大小：684K
• 年卷期：v.52,no.14(July 15, 2013)
• ISSN：1520-510X

文摘

A quantum chemical study of the photocatalytic dimerization of 伪-methylstyrene catalyzed by a dinuclear ruthenium鈥損alladium complex was performed at the DFT/TD-DFT level in order to find the key steps of the catalytic reaction. This study reveals that the second insertion of 伪-methylstyrene is the rate-determining step and that it proceeds via triplet excited states of an intermediate complex. These excited states have geometries significantly different from that of the reactant, especially within the coordination sphere of the Pd unit. Indeed, one Pd鈥揷arbon bond is considerably lengthened, favoring the insertion process. These results open up the possibilities to optimize the process by fine modulation of the catalyst structure.