Synthesis and Reactivity of Trivalent Tp*U(CH2Ph)2(THF): Insertion vs Oxidation at Low-Valent Uranium鈥揅arbon Bonds

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• 作者：Ellen M. Matson ; William P. Forrest ; Phillip E. Fanwick ; Suzanne C. Bart
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 11, 2013
• 年：2013
• 卷：32
• 期：5
• 页码：1484-1492
• 全文大小：421K
• 年卷期：v.32,no.5(March 11, 2013)
• ISSN：1520-6041

文摘

The synthesis of a rare uranium(III) bis(benzyl), Tp*U(CH₂Ph)₂(THF) (2), was achieved by salt metathesis of Tp*UI₂(THF)₂ with 2 equiv of KCH₂Ph at low temperature. This was characterized by p>1p>H NMR, infrared, and electronic absorption spectroscopy as well as X-ray crystallography. Addition of benzophenone to 2 forms the uranium(IV) radical coupling product Tp*U(CH₂Ph)₂(OC(Ph)₂CH₂Ph) (3), whereas N₃Mes produces the imido derivative Tp*U(NMes)(CH₂Ph)(THF) (4). Adding a further 1 equiv of N₃Mes to tetravalent 4 results in U鈥揅 insertion to form the U(IV) triazenido species Tp*U(NMes)[(CH₂Ph)N₃(Mes)-魏p>2p>Np>1,2p>](THF) (5). Compound 2 also reacts with the redox-active 4,6-di-tert-butyl-2-[(2,6-diisopropylphenyl)imino]quinone (p>DIPPp>iq) to form the oxidized amido(phenolate) Tp*U(CH₂Ph)(p>DIPPp>ap) (6).