Synthesis of Group 4 Metal Complexes Stabilized by an Amine-Bridged Bis(phenolato) Ligand and Their Catalytic Behavior in Intermolecular Hydroamination Reactions

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• 作者：Qiu Sun ; Yaorong Wang ; Dan Yuan ; Yingming Yao ; Qi Shen
• 刊名：Organometallics
• 出版年：2014
• 出版时间：February 24, 2014
• 年：2014
• 卷：33
• 期：4
• 页码：994-1001
• 全文大小：440K
• 年卷期：v.33,no.4(February 24, 2014)
• ISSN：1520-6041

文摘

Zirconium and titanium complexes 1 and 2, bearing an amine-bridged bis(phenolato) ligand, have been synthesized and characterized. Although 1 and 2 were inactive in catalyzing intermolecular hydroamination reactions, cationic complexes generated in situ from treatment of 1 and 2 with borate [Ph₃C][B(C₆F₅)₄], respectively, were found to be highly active. In general, excellent yields (up to >99%) and 100% regioselectivity for a broad range of terminal alkynes and anilines were observed within a reaction time of 1 h. Reactions with internal alkynes of moderate sterics also led to good yields and moderate regioselectivity. A kinetic study was also conducted, which provided some insights into the mechanism of hydroamination reactions.