Mechanistic Studies on the Carboxylation of Hafnocene and ansa-Zirconocene Dinitrogen Complexes with CO2

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• 作者：Xuelu Ma ; Yanhui Tang ; Ming Lei
• 刊名：Organometallics
• 出版年：2013
• 出版时间：December 9, 2013
• 年：2013
• 卷：32
• 期：23
• 页码：7077-7082
• 全文大小：472K
• 年卷期：v.32,no.23(December 9, 2013)
• ISSN：1520-6041

文摘

A DFT study on the carboxylation of hafnocene and ansa-zirconocene dinitrogen complexes with CO₂ indicates that the most favorable initial CO₂ insertion into M鈥揘 (M = Hf, Zr) proceeds by a stepwise path rather than a concerted [2 + 2] path. The calculated results explain the regioselectivity of the N鈥揅 formation in experiments. In addition, a comparative analysis of ring tension and charge distribution unveils the different activities of N鈥揘 bond cleavage in the CO and CO₂ direct N鈥揅 bond formation reactions.