Ping-Pong at Gold: Proton Jump Between Coordinated Phenyl and η1-Benzene Ligands, A Computational Study

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• 作者：Manik Kumer Ghosh ; Mats Tilset ; Ajay Venugopal ; Richard H. Heyn ; Ole Swang
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：August 12, 2010
• 年：2010
• 卷：114
• 期：31
• 页码：8135-8141
• 全文大小：324K
• 年卷期：v.114,no.31(August 12, 2010)
• ISSN：1520-5215

文摘

A DFT computational investigation predicts that the Au(III) complex (bpy)Au(C₆H₅)²⁺ reacts with benzene to furnish square planar (bpy)Au(C₆H₅)(η¹-C₆H₆)²⁺. Intramolecular processes that occur within this species have been located, and the energetics of all processes have been quantified. The dynamic processes that have been identified are (1) benzene ring rotation with respect to Au, (2) direct hydrogen transfer from the benzene to the phenyl ligand, (3) hydrogen transfer from the ipso to the ortho positions in the coordinated benzene ligand, and (4) hydrogen transfer from the benzenium ligand formed by the ipso/ortho isomerization to the phenyl ligand. Similarities and differences are seen between the behavior of (bpy)Au(C₆H₅)(η¹-C₆H₆)²⁺ and previously reported isoelectronic Pt(II) complexes. Preliminary experimental results related to this chemistry are reported, and possible consequences for C−H bond activation mediated by gold are discussed.