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• 作者：Michael K. Takase ; Nathan A. Siladke ; Joseph W. Ziller ; William J. Evans
• 刊名：Organometallics
• 出版年：2011
• 出版时间：February 14, 2011
• 年：2011
• 卷：30
• 期：3
• 页码：458-465
• 全文大小：1031K
• 年卷期：v.30,no.3(February 14, 2011)
• ISSN：1520-6041

文摘

[(C₅Me₅)(C₈H₈)U(渭-OTf)]₂, 1 (OTf = OSO₂CF₃), reacts with LiMe to form the metathesis product (C₅Me₅)(C₈H₈)UMe, 2, as well as the product of a methyl C鈭扝 activation, (C₈H₈)(C₅Me₄CH₂)U, 3. Methane was observed in the ¹H NMR spectrum of the reaction mixture, which is consistent with the metalation of a (C₅Me₅)^{鈭?/sup> ligand by the uranium methyl group in 2. Complex 2 was identified in this reaction mixture by addition of iPrN鈺怌鈺怤iPr to form the previously reported (C₅Me₅)(C₈H₈)U[iPrNC(Me)NiPr-魏2N,N鈥瞉, 4. The reactions of 1 with LiEt and LiCH₂CMe₃ similarly form mixtures at room temperature that contain 3 and compounds with 1H NMR spectra consistent with (C₅Me₅)(C₈H₈)UEt, 5, and (C₅Me₅)(C₈H₈)U(CH₂CMe₃), 6, respectively. Complexes 2, 5, and 6 convert to 3 after 24 h at 100 掳C. Complex 3 can also be synthesized at 100 掳C from (C₅Me₅)(C₈H₈)UPh, 7, and was characterized as the THF adduct of a 鈥渢uck-in鈥?complex, (畏8-C₈H₈)(畏5:畏1-C₅Me₄CH₂)U(THF), 8, by X-ray crystallography. Complex 3 allowed the insertion chemistry of an isolable f element (畏5:畏1-C₅Me₄CH₂)2鈭?/sup> metallocene complex to be studied for the first time and provides access to new heteroleptic tethered metallocenes. iPrN鈺怌鈺怤iPr inserts into the U鈭扖(畏1-C₅Me₄CH₂) bond of 3 to form the amidinate complex (C₈H₈)[C₅Me₄CH₂C(NiPr)₂]U, 9. tBuN鈮 reacts in a series of steps through intermediates such as (C₈H₈)(C₅Me₄CH₂C鈺怤tBu)U, 10, and (C₈H₈)(C₅Me₄CH₂C鈺怤tBu)U(C鈮tBu) that leads to the isolation of the isocyanide double-insertion product, (畏8-C₈H₈)[畏5-C₅Me₄CH₂C(鈺怌鈺怤tBu)NtBu-魏N]U, 11.}