Reactivity of Scorpionate-Anchored Yttrium Alkyl Primary Amido Complexes toward Carbodiimides. Insertion Selectivity of Y鈥揘HAr and Y鈥揅H2Ph Bonds

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• 作者：Weiyin Yi ; Shujian Huang ; Jie Zhang ; Zhenxia Chen ; Xigeng Zhou
• 刊名：Organometallics
• 出版年：2013
• 出版时间：October 14, 2013
• 年：2013
• 卷：32
• 期：19
• 页码：5409-5415
• 全文大小：347K
• 年卷期：v.32,no.19(October 14, 2013)
• ISSN：1520-6041

文摘

The Tp^Me2-supported yttrium dialkyl Tp^Me2Y(CH₂Ph)₂(THF) (Tp^Me2 = tri(3,5-dimethylpyrazolyl)borate) reacted with 1 equiv of ArNH₂ in THF at room temperature to afford the yttrium alkyl primary amido complexes Tp^Me2YNHAr(CH₂Ph)(THF) (Ar = Ph (1), C₆H₃-ⁱPr₂-2,6 (2)) in 84% and 88% isolated yields, respectively. Complex 1 reacted with ⁱPrN鈺怌鈺怤ⁱPr in THF at room temperature to give a yttrium dianionic guanidinate complex, Tp^Me2Y[(ⁱPrN)₂C鈺怤Ph](THF)₂ (3, 74%). However, the reaction of 1 with ArN鈺怌鈺怤Ar (Ar = C₆H₃-ⁱPr₂-2,6) in the same conditions produced a Y鈥揅 bond insertion product, Tp^Me2Y[(ArN)₂CCH₂Ph](NHPh) (4, 87%). Moreover, treatment of 2 with 1 equiv of ⁱPrN鈺怌鈺怤ⁱPr in THF at room temperature afforded two yttrium complex, Tp^Me2Y[(ⁱPrN)C鈺怤Ar](THF) (5) and Tp^Me2Y[(ⁱPrN)₂CCH₂Ph](NHAr) (6), in 58% and 19% isolated yields, respectively. These results indicated that carbodiimide can selectively insert into the Y鈥揅H₂Ph and Y鈥揘HAr 蟽-bonds of Tp^Me2-supported yttrium alkyl primary amido complexes Tp^Me2YNHAr(CH₂Ph)(THF), and this selectivity depends on the steric hindrance of the substituent groups R of cabodiimides and the primary amido ligands. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures except 1 were also confirmed by single-crystal X-ray diffraction analysis.