Highly Reactive Scandium Phosphinoalkylidene Complex: C–H and H–H Bonds Activation

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• 作者：Weiqing Mao ; Li Xiang ; Carlos Alvarez Lamsfus ; Laurent MaronXuebing Leng ; Yaofeng Chen
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 25, 2017
• 年：2017
• 卷：139
• 期：3
• 页码：1081-1084
• 全文大小：338K
• ISSN：1520-5126

文摘

The first scandium phosphinoalkylidene complex was synthesized and structurally characterized. The complex has the shortest Sc–C bond lengths reported to date (2.089(3) Å). DFT calculations reveal the presence of a three center π interaction in the complex. This scandium phosphinoalkylidene complex undergoes intermolecular C–H bond activation of pyridine, 4-dimethylamino pyridine and 1,3-dimethylpyrazole at room temperature. Furthermore, the complex rapidly activates H₂ under mild conditions. DFT calculations also demonstrate that the C–H activation of 1,3-dimethylpyrazole is selective for thermodynamic reasons and the relatively slow reaction is due to the need of fully breaking the chelating effect of the phosphino group to undergo the reaction whereas this is not the case for H₂.