Sequential Nitrene Transfers to an Organometallic Half-Sandwich Iridium Complex

详细信息    查看全文

• 作者：Christopher R. Turlington ; Peter S. White ; Maurice Brookhart ; Joseph L. Templeton
• 刊名：Organometallics
• 出版年：2015
• 出版时间：October 26, 2015
• 年：2015
• 卷：34
• 期：20
• 页码：4810-4812
• 全文大小：230K
• ISSN：1520-6041

文摘

Nitrene transfer to an iridium(Cp*) complex with a pyridyl-amide bidentate ligand drives an unexpected outer-sphere C鈥揌 activation and amide functionalization reaction mediated by this metal center. This is a significant departure from C鈥揘 bond-forming processes in mononuclear rhodium and iridium catalysts, which require C鈥揌 activation at the metal center prior to nitrene transfer and insertion (an inner-sphere C鈥揌 insertion pathway). The mechanism likely involves a high oxidation state iridium-imido reactive species capable of hydrogen atom abstraction and a radical-based rearrangement during the formation of the ultimate iridium product.