Oxidative Coupling in the Reaction of TpMe2Ir(2,3-dimethylbutadiene) with Diphenylacetylene

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• 作者：Margarita Paneque ; Cristina M. Posadas ; Manuel L. Poveda ; Nuria Rend&oacute ; n ; Kurt Mereiter
• 刊名：Organometallics
• 出版年：2007
• 出版时间：April 9, 2007
• 年：2007
• 卷：26
• 期：8
• 页码：1900 - 1906
• 全文大小：188K
• 年卷期：v.26,no.8(April 9, 2007)
• ISSN：1520-6041

文摘

The 2,3-dimethylbutadiene complex Tp^Me2Ir(CH₂=C(Me)C(Me)=CH₂) (1) reacts with PhCmages/entities/tbd1.gif">CPh, inC₆H₁₂ at 60 mages/entities/deg.gif">C, with coupling of the diene and the alkyne and formation of compound 2a, which containsan elaborated bicyclic chelating ligand with alkyl and mages/gifchars/eta.gif" BORDER=0 >³-allyl functionalities. NCMe reacts reversiblywith 2a, giving rise to a mixture of the isomeric iridacyclopentenes m060967xa10001">Tp^Me2m060967x00000">Ir(CH₂C(Me)(CMe=CH₂)C(Ph)=C(Ph))(NCMe) (3) and m060967xa10002">Tp^Me2m060967x00000">Ir(CH₂C(Me)(cis-CPh=CHPh)C(Me)=CH)(NCMe) (4). Complex 2adecomposes in C₆H₁₂ at 80 mages/entities/deg.gif">C to give a complex mixture from which an interesting substituted iridafulvene,5, has been isolated by chromatography. All these compounds have been characterized by NMRspectroscopy and X-ray crystallography. Possible reaction mechanisms for the formation of these speciesare discussed.