Theoretical Study on Iridacycle and Rhodacycle Formation via C鈥揌 Activation of Phenyl Imines

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• 作者：Jing Li ; Wei Hu ; Yiming Peng ; Yaomou Zhang ; Junda Li ; Wenxu Zheng
• 刊名：Organometallics
• 出版年：2014
• 出版时间：May 12, 2014
• 年：2014
• 卷：33
• 期：9
• 页码：2150-2159
• 全文大小：556K
• 年卷期：v.33,no.9(May 12, 2014)
• ISSN：1520-6041

文摘

A computational study with the Becke3LYP DFT functional was carried out on the formation of iridacycles and rhodacycles through C鈥揌 activation of phenyl imines in methanol solvent. The whole catalytic pathway was proposed and verified, starting from the catalyst [Cp*MCl₂]₂ cleavage and ending with the cyclometalated complex. The five most important issues, namely, chloride dissociation and C鈥揌 activation precursor formation, aromatic C鈥揌 bond activation, the reaction rate difference between the Ir and Rh systems, the nature of regioselectivity, and the role of the protic solvent are discussed. The calculations indicate that the C鈥揌 bond activation by the transition metal iridium is kinetically and thermodynamically more favorable than that by rhodium, and the regioselectivity of the reaction has been determined both electronically and sterically.