Trapping of Anionic Organic Radicals by (TpMe2)2Ln (Ln = Sm, Eu)

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• 作者：&Acirc ; ngela Domingos ; Irene Lopes ; Jo&atilde ; o C. Waerenborgh ; No&eacute ; mia Marques ; G.Y. Lin ; X.W. Zhang ; Josef Takats ; Robert McDonald ; Anna C. Hillier ; Andrea Sella ; Mark R. J. Elsegood ; Victor W.
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：October 29, 2007
• 年：2007
• 卷：46
• 期：22
• 页码：9415 - 9424
• 全文大小：256K
• 年卷期：v.46,no.22(October 29, 2007)
• ISSN：1520-510X

文摘

Stoichiometric reaction of [Sm(Tp^Me2)₂], 1, with a variety of reducible ketone- and quinone-type substrates gavethermally stable, isolable radical anions/ketyls in moderate to good yields. Thus reaction with benzophenone gave[Sm(Tp^Me2)₂(OCPh₂)], 2, with fluorenone [Sm(Tp^Me2)₂(¹-OC₁₃H₈)], 3, and di-tert-butylparaquinone [Sm(Tp^Me2)₂(¹-OC₆H₂(^tBu)₂O)], 4, each of which was structurally characterized. In the case of the less-hindered benzoquinone, anunimetallic semiquinone [Sm(Tp^Me2)₂(OC₆H₄O)], 5, could be isolated, although it was unstable with respect to formationof the dimetallic complex [Sm(Tp^Me2)₂]₂(-OC₆H₄O), 6. Compound 6 was structurally characterized, as was itsanthraquinone analogue [Sm(Tp^Me2)₂]₂(-OC₁₄H₈O), 7. When the analogous reaction was carried out between theless-reducing [Eu(Tp^Me2)₂] and benzoquinone, only the europium analogue of the semiquinone 5, [Eu(Tp^Me2)₂(OC₆H₄O)], 8, could be isolated. The use of the sterically hindered 3,5-di-tert-butyl-o-benzoquinone allowed isolationof [Sm(Tp^Me2)₂(DTBSQ)], 9.