Site-Selective Alkyl Dehydrogenation of a Coordinated Acylphosphine Ligand

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• 作者：Sean M. Whittemore ; Ryan J. Yoder ; James P. Stambuli
• 刊名：Organometallics
• 出版年：2012
• 出版时间：September 10, 2012
• 年：2012
• 卷：31
• 期：17
• 页码：6124-6130
• 全文大小：409K
• 年卷期：v.31,no.17(September 10, 2012)
• ISSN：1520-6041

文摘

Regio- and stereoselective alkane dehydrogenation is a difficult challenge in organometallic chemistry. Intermolecular reactions of this type typically produce numerous olefin stereo- and regioisomers. Herein, we report our initial investigations into the intramolecular dehydrogenation of a datively bound alkyl ligand, demonstrating the first example of a site-selective dehydrogenation of an unactivated acyclic alkyl group. The alkyl group is located on an acylphosphine ligand that is coordinated to a Cp*IrCl₂ monomer. A mechanistic proposal, guided by the isolation of a dimeric iridium complex and supported by computational results, is also described.