Dinitrogen Activation by Dihydrogen and a PNP-Ligated Titanium Complex

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• 作者：Baoli Wang ; Gen Luo ; Masayoshi Nishiura ; Shaowei Hu ; Takanori Shima ; Yi Luo ; Zhaomin Hou
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：February 8, 2017
• 年：2017
• 卷：139
• 期：5
• 页码：1818-1821
• 全文大小：306K
• ISSN：1520-5126

文摘

The hydrogenolysis of the PNP-ligated titanium dialkyl complex {(PNP)Ti(CH₂SiMe₃)₂} (1, PNP = N(C₆H₃-2-PⁱPr₂-4-CH₃)₂) with H₂ (1 atm) in the presence of N₂ (1 atm) afforded a binuclear titanium side-on/end-on dinitrogen complex {[(PNP)Ti]₂(μ₂,η¹,η²-N₂)(μ₂-H)₂} (2) at room temperature, which upon heating at 60 °C with H₂ gave a μ₂-imido/μ₂-nitrido/hydrido complex {[(PNP)Ti]₂(μ₂-NH)(μ₂-N)H} (3) through the cleavage and partial hydrogenation of the N₂ unit. The mechanistic aspects of the hydrogenation of the N₂ unit in 2 with H₂ have been elucidated by the density functional theory calculations.