Piano-Stool Lutetium Amido and Imido Compounds Supported by a Constrained Bis(oxazoline)cyclopentadienyl Ligand

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• 作者：Nicole L. Lampland ; Jing Zhu ; Megan Hovey ; Barun Jana ; Arkady Ellern ; Aaron D. Sadow
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6938-6946
• 全文大小：507K
• ISSN：1520-510X

文摘

{Bo^MCp^tet}Lu(CH₂Ph)₂ (1; Bo^MCp^tet = MeC(Ox^Me2)₂C₅Me₄; Ox^Me2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo^MCp^tetH and Lu(CH₂Ph)₃THF₃. Compound 1 reacts with 1 or 2 equiv of H₂NCH₂R (R = C₆H₅, 1-C₁₀H₇) to give the corresponding imido complexes [{Bo^MCp^tet}LuNCH₂R]₂ (R = C₆H₅ (2a), 1-C₁₀H₇ (2b)) or amido complexes {Bo^MCp^tet}Lu(NHCH₂R)₂ (R = C₆H₅ (3a), 1-C₁₀H₇ (3b)). Once isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{Bo^MCp^tet}LuNCH₂(1-C₁₀H₇)]₂ in the solid state. The reaction of 1 and NH₃B(C₆F₅)₃ affords crystallographically characterized {Bo^MCp^tet}Lu{NHB(C₆F₅)₂}C₆F₅. This species is proposed to form via a transient lutetium imido, which undergoes C₆F₅ migration to the lutetium center.